CN117024866A - Preparation method of PE regenerated plastic particles - Google Patents
Preparation method of PE regenerated plastic particles Download PDFInfo
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- CN117024866A CN117024866A CN202310997109.6A CN202310997109A CN117024866A CN 117024866 A CN117024866 A CN 117024866A CN 202310997109 A CN202310997109 A CN 202310997109A CN 117024866 A CN117024866 A CN 117024866A
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- auxiliary agent
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- recycled plastic
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- 229920003023 plastic Polymers 0.000 title claims abstract description 54
- 239000004033 plastic Substances 0.000 title claims abstract description 54
- 239000002245 particle Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004698 Polyethylene Substances 0.000 claims abstract description 46
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 34
- 229920000573 polyethylene Polymers 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 polyethylene Polymers 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 238000005469 granulation Methods 0.000 claims abstract description 11
- 230000003179 granulation Effects 0.000 claims abstract description 11
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- RQJDUEKERVZLLU-UHFFFAOYSA-N 4-Hydroxybenzylamine Chemical compound NCC1=CC=C(O)C=C1 RQJDUEKERVZLLU-UHFFFAOYSA-N 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000013067 intermediate product Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- YLZQHQUVNZVGOK-UHFFFAOYSA-N 2-methylnon-1-ene Chemical compound CCCCCCCC(C)=C YLZQHQUVNZVGOK-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000543 intermediate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 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 abstract description 10
- 239000003063 flame retardant Substances 0.000 abstract description 10
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract description 8
- 239000004480 active ingredient Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003712 anti-aging effect Effects 0.000 abstract description 4
- 239000003963 antioxidant agent Substances 0.000 abstract description 4
- 230000003078 antioxidant effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- FDKXTQMXEQVLRF-ZHACJKMWSA-N (E)-dacarbazine Chemical compound CN(C)\N=N\c1[nH]cnc1C(N)=O FDKXTQMXEQVLRF-ZHACJKMWSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- 241000252229 Carassius auratus Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 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
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- ZONVIFVBWLLLNU-UHFFFAOYSA-H dialuminum hexaphenoxide Chemical compound [O-]C1=CC=CC=C1.[Al+3].[Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZONVIFVBWLLLNU-UHFFFAOYSA-H 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical compound [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/304—Aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of PE regenerated plastic particles, which belongs to the technical field of regenerated plastic and comprises the following steps: weighing polyethylene resin, an initiator and a compatibilizer according to a proportion, sequentially adding the mixture into a reaction kettle, introducing nitrogen, stirring for reaction, and then extruding and granulating to obtain master batch; and uniformly mixing the recycled polyethylene, the master batch and the auxiliary agent, and carrying out melt extrusion, granulation and drying to obtain PE regenerated plastic particles. In order to improve the performance of PE regenerated plastics, the synthetic auxiliary agent is added, the auxiliary agent molecule contains a hindered phenol structure, a phosphate structure and two long fatty chains, the hindered phenol structure belongs to an antioxidant anti-aging active ingredient, the phosphate structure belongs to a flame-retardant active ingredient, and the existence of the long fatty chains can promote the uniform dispersion of the auxiliary agent in the plastics, so that the effect of 1+1>2 is realized by adding the auxiliary agent, and the PE regenerated plastics has very important application value.
Description
Technical Field
The invention belongs to the technical field of recycled plastics, and particularly relates to a preparation method of PE recycled plastic particles.
Background
Polyethylene (PE) is a typical commercial polymer with many fields of application and with a significant growth rate. The reason for this is not only the favorable cost performance, but also the universality of the material, and can be widely applied to the fields of automobiles, packaging, daily necessities, pipes and the like.
With the application of polyethylene products, waste plastics are generated, and the waste reclaimed materials are recycled, so that the environmental pollution problem caused by the plastics can be relieved to a certain extent, and petroleum resources can be saved. Meanwhile, compared with new materials, the regenerated materials are dominant in price, but the molecular weight of the regenerated materials is reduced due to the influence of ultraviolet irradiation, oxidization and the like in the processes of multiple processing and use, and the problems of poor processing performance, such as goldfish eye bubbles and the like, poor toughness, strength and the like in the processing process are further represented, the recovery processing of the regenerated materials is seriously influenced, and the service performance of products cannot be met.
In order to make the regenerated plastic meet the service performance, a plurality of additives (such as compatilizer, antioxidant, flame retardant and the like) are often added into the plastic in the prior art, on one hand, the components are difficult to fully and uniformly mix due to the plurality of additives, and the performance improving effect is further affected; on the other hand, the addition of various additives can have a negative effect on the properties of the plastic itself. Therefore, a more effective way for improving the performance of PE regenerated plastics is sought, and the method has very important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of PE regenerated plastic particles.
In order to improve the performance of PE regenerated plastics, the synthetic auxiliary agent is added, the auxiliary agent molecule contains a hindered phenol structure, a phosphate structure and two long fatty chains, the hindered phenol structure belongs to an antioxidant anti-aging active ingredient, the phosphate structure belongs to a flame-retardant active ingredient, and the existence of the long fatty chains can promote the uniform dispersion of the auxiliary agent in the plastics, so that the effect of 1+1>2 is realized by adding one auxiliary agent, the phenomenon that the auxiliary agent is difficult to mix uniformly caused by adding various additives can be prevented, the performances of the regenerated plastics can be obviously improved, and the PE regenerated plastics have very important application value.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the PE regenerated plastic particles comprises the following steps:
firstly, weighing polyethylene resin, an initiator and a compatibilizer according to a proportion, sequentially adding the mixture into a reaction kettle, introducing nitrogen, stirring and reacting for 3-4 hours at the temperature of 90-100 ℃, cooling, and then feeding the mixture into a double-screw extruder for extrusion granulation to obtain master batch;
because the recycled polyethylene is not generally pure polyethylene, and is doped with other types of polymers or impurities, the effective fusion phenomenon of various components in the recycled polyethylene can be improved through the preparation of master batches, and the service performance of the recycled plastic is improved;
and secondly, uniformly mixing the recycled polyethylene, the master batch and the auxiliary agent, and carrying out melt extrusion, granulation and drying to obtain PE regenerated plastic particles.
Further, the compatibilizer is a mixture of maleic anhydride and glycidyl methacrylate according to a mass ratio of 3:1.
Further, the initiator is dibenzoyl peroxide or tert-butyl hydroperoxide.
Further, the mass ratio of the polyethylene resin, the initiator and the compatibilizer in the first step is 100:2-3:18-20.
Further, the mass ratio of the polyethylene, the master batch and the auxiliary agent recovered in the second step is 100:2-3:4-6.
Further, the auxiliary agent is prepared by the following steps:
s1, adding 4-hydroxybenzylamine, granular aluminum and triphenoxyaluminum into an autoclave, heating to 150 ℃ and preserving heat for 3 hours, then adding 2-methyl-1-nonene into the autoclave, reacting for 3 hours at 130 ℃, cooling, treating with a small amount of hydrochloric acid, separating liquid (removing aluminum hydrate salt), taking an organic phase, adding deionized water, uniformly mixing, extracting with ethyl acetate, taking the organic phase, drying with anhydrous magnesium sulfate, filtering, and removing ethyl acetate by rotary evaporation to obtain an intermediate product; the ratio of the amounts of 4-hydroxybenzylamine, granular aluminum, triphenoxyaluminum, 2-methyl-1-nonene used was 0.1mol:0.1g:50mg:0.21mol;
under the catalysis of aluminum and triphenoxyaluminum under a certain pressure, 4-hydroxybenzylamine and 2-methyl-1-nonene react chemically to obtain an intermediate product, and the reaction process is as follows:
s2, adding DIC (N, N-diisopropylcarbodiimide), 2-carboxyethyl phenyl hypophosphorous acid and DMF (N, N-dimethylformamide) into a three-neck flask with a stirring device, introducing nitrogen for protection, stirring and dissolving uniformly, adding an intermediate product and triethylamine into the system, and heating at room temperature and N 2 Stirring under protection for reaction for 3 hours, after the reaction is finished, distilling under reduced pressure to remove most of solvent DMF, adding deionized water into a product, mixing uniformly, extracting the mixture with toluene, taking an organic layer, drying with anhydrous magnesium sulfate, filtering, and removing toluene by rotary evaporation under reduced pressure to obtain an auxiliary agent; DIC, 2-carboxyethylphenyl hypophosphorous acid, DMF, intermediates, triethylamine in an amount of 13.2g:0.105mol:300mL:40.3g:10.1g;
under the action of DIC and triethylamine, the-COOH on the 2-carboxyethylphenyl hypophosphorous acid molecule and the-NH on the intermediate product molecule 2 Amidation reaction to obtain assistant, the reaction process is as follows:
the obtained auxiliary agent contains a hindered phenol structure, a phosphate structure and two long fatty chains on the molecule; the hindered phenol structure is easier to provide protons than the polymer, namely, more favorable reaction is provided to form phenoxy free radicals, so that the polymer is relatively stable and cannot undergo further oxidation, in addition, the hindered phenol structure can also perform some reactions for capturing carbon free radicals, the free radicals in the formula can form dimers, and the dimers can react with peroxide free radicals to deactivate the dimers and become stable quinone molecules, so that the ageing of plastics is delayed, and the anti-oxidation and anti-aging effects are achieved; the phosphate structure belongs to a phosphorus flame-retardant component, has safe and pollution-free flame retardant performance, and plays a role in improving the flame retardant performance of plastics; in addition, the long fatty chain contained on the plastic has high flexibility and extremely high compatibility with the PE matrix, so that the obtained auxiliary agent can be uniformly dispersed in the plastic, the plastic can obtain uniform and effective ageing resistance and flame retardance, and the uniform distribution can better exert all properties of the auxiliary agent.
Further, the triphenoxyaluminum is prepared by the steps of: adding metal aluminum (aluminum strips or aluminum sheets) into phenol, heating to 160 ℃, and reacting for 3 hours to generate triphenoxyaluminum (catalyst); the dosage ratio of metallic aluminum to phenol was 1g:150g.
Further, the pressure in the autoclave in step S1 is set to 16-18kg/cm 2 。
The aluminum phenolate (triphenoxyaluminum) has high catalytic activity, and can be connected with olefin at two ortho positions of phenolic hydroxyl by combining the pressure in the reaction kettle, so that an intermediate product is obtained.
The invention has the beneficial effects that:
in order to improve the performance of PE regenerated plastics, the synthetic auxiliary agent is added, the auxiliary agent molecule contains a hindered phenol structure, a phosphate structure and two long fatty chains, the hindered phenol structure belongs to an antioxidant anti-aging active ingredient, the phosphate structure belongs to a flame-retardant active ingredient, and the existence of the long fatty chains can promote the uniform dispersion of the auxiliary agent in the plastics, so that the effect of 1+1>2 is realized by adding one auxiliary agent, the phenomenon that the auxiliary agent is difficult to mix uniformly caused by adding various additives can be prevented, the performances of the regenerated plastics can be obviously improved, and the PE regenerated plastics have very important application value.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, 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 triphenoxyaluminum:
0.1g of aluminum metal flake was added to 15g of phenol, heated to 160℃and reacted for 3 hours to give aluminum triphenoxide.
Example 2
Preparing an auxiliary agent:
s1, adding 0.1mol of 4-hydroxybenzylamine, 0.1g of granular aluminum and 50mg of triphenoxyaluminum prepared in example 1 into an autoclave, heating to 150 ℃ and preserving heat for 3 hours, then adding 0.21mol of 2-methyl-1-nonene into the autoclave, reacting for 3 hours at 130 ℃, cooling, then treating with a small amount of hydrochloric acid, separating liquid (removing aluminum hydrate salt), taking an organic phase, adding deionized water, uniformly mixing, extracting with ethyl acetate, taking the organic phase, drying with anhydrous magnesium sulfate, filtering, and removing ethyl acetate by rotary evaporation to obtain an intermediate product;
s2, adding 13.2g of DIC, 0.105mol of 2-carboxyethyl phenyl hypophosphorous acid and 300mL of DMF into a three-necked flask with a stirring device, introducing nitrogen for protection, stirring and dissolving uniformly, adding 40.3g of intermediate product and 10.1g of triethylamine into the system, and adding the mixture into the system at room temperature and N 2 Stirring under protection for reaction for 3 hours, after the reaction is finished, distilling under reduced pressure to remove most of solvent DMF, adding deionized water into the product, mixing uniformly, extracting the mixture with toluene, taking an organic layer, drying with anhydrous magnesium sulfate, filtering, and removing toluene by rotary evaporation under reduced pressure to obtain the auxiliary agent.
Example 3
Preparing an auxiliary agent:
s1, adding 0.2mol of 4-hydroxybenzylamine, 0.3g of granular aluminum and 100mg of triphenoxyaluminum prepared in example 1 into an autoclave, heating to 150 ℃ and preserving heat for 3 hours, then adding 0.42mol of 2-methyl-1-nonene into the autoclave, reacting for 3 hours at 130 ℃, cooling, then treating with a small amount of hydrochloric acid, separating liquid (removing aluminum hydrate salt), taking an organic phase, adding deionized water, uniformly mixing, extracting with ethyl acetate, taking the organic phase, drying with anhydrous magnesium sulfate, filtering, and removing ethyl acetate by rotary evaporation to obtain an intermediate product;
s2, adding 26.4g of DIC, 0.21mol of 2-carboxyethyl phenyl hypophosphorous acid and 600mL of DMF into a three-necked flask with a stirring device, introducing nitrogen for protection, stirring and dissolving uniformly, adding 80.6g of intermediate product and 20.2g of triethylamine into the system, and adding the mixture into the system at room temperature and N 2 Stirring under protection for reaction for 3 hours, after the reaction is finished, distilling under reduced pressure to remove most of solvent DMF, adding deionized water into the product, mixing uniformly, extracting the mixture with toluene, taking an organic layer, drying with anhydrous magnesium sulfate, filtering, and removing toluene by rotary evaporation under reduced pressure to obtain the auxiliary agent.
Example 4
The preparation method of the PE regenerated plastic particles comprises the following steps:
firstly, sequentially adding 1000g of polyethylene resin, 20g of dibenzoyl peroxide and 180g of a compatibilizer into a reaction kettle, introducing nitrogen, stirring and reacting for 3 hours at the temperature of 90 ℃, cooling, and then feeding into a double-screw extruder for extrusion granulation to obtain master batch;
wherein the compatibilizer is a mixture of maleic anhydride and glycidyl methacrylate according to a mass ratio of 3:1;
and secondly, uniformly mixing 1000g of recycled polyethylene, 25g of master batch and 40g of auxiliary agent prepared in example 2, and carrying out melt extrusion, granulation and drying to obtain PE regenerated plastic particles.
Example 5
The preparation method of the PE regenerated plastic particles comprises the following steps:
firstly, sequentially adding 1000g of polyethylene resin, 25g of tert-butyl hydroperoxide and 190g of a compatibilizer into a reaction kettle, introducing nitrogen, stirring and reacting for 3.5 hours at the temperature of 95 ℃, cooling, and then feeding into a double-screw extruder for extrusion granulation to obtain master batch;
wherein the compatibilizer is a mixture of maleic anhydride and glycidyl methacrylate according to a mass ratio of 3:1;
and secondly, uniformly mixing 1000g of recycled polyethylene, 25g of master batch and 50g of auxiliary agent prepared in example 3, and carrying out melt extrusion, granulation and drying to obtain PE regenerated plastic particles.
Example 6
The preparation method of the PE regenerated plastic particles comprises the following steps:
firstly, sequentially adding 1000g of polyethylene resin, 30g of dibenzoyl peroxide and 200g of a compatibilizer into a reaction kettle, introducing nitrogen, stirring and reacting for 4 hours at the temperature of 100 ℃, cooling, and then feeding into a double-screw extruder for extrusion granulation to obtain master batch;
wherein the compatibilizer is a mixture of maleic anhydride and glycidyl methacrylate according to a mass ratio of 3:1;
and secondly, uniformly mixing 1000g of recycled polyethylene, 30g of master batch and 60g of auxiliary agent prepared in example 2, and carrying out melt extrusion, granulation and drying to obtain PE regenerated plastic particles.
Comparative example
The auxiliary material in example 4 was removed, and the remaining materials and the preparation process were unchanged to obtain plastic particles.
The plastics obtained in examples 4-6 and comparative examples were injection molded, cut into test specimens and subjected to the following performance tests:
the mechanical properties are measured by reference to the standard method in GB/T1040-2006;
notched impact strength was determined by reference to the standard method of GB/T1843-2008;
flame retardancy was tested according to the UL-94 standard;
glowing filament flame retardant properties were tested according to IEC 60695-2-12-2000;
the thermal-oxidative aging resistance is tested according to GB/T2951.1-1994, the oxidation induction period (OIT) is measured by adopting a differential scanning calorimeter, the test condition is that under the protection of nitrogen, the temperature is raised at 20 ℃/min, the temperature is kept constant for 5min after the temperature is raised to 200 ℃, the nitrogen is replaced by oxygen, and the temperature is lowered at 20 ℃/min.
The results are shown in the following table:
as can be seen from the data in the table, the PE regenerated plastic obtained by the invention has high mechanical properties and excellent flame retardant property and ageing resistance; the data of the comparative example show that the addition of the auxiliary agent not only can remarkably improve the flame retardant property and the ageing resistance of the plastic, but also can improve the mechanical property of the plastic to a certain extent.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (9)
1. The preparation method of the PE regenerated plastic particles is characterized by comprising the following steps of:
firstly, weighing polyethylene resin, an initiator and a compatibilizer according to a proportion, sequentially adding the mixture into a reaction kettle, introducing nitrogen, stirring and reacting for 3-4 hours at the temperature of 90-100 ℃, cooling, and then feeding the mixture into a double-screw extruder for extrusion granulation to obtain master batch;
and secondly, uniformly mixing the recycled polyethylene, the master batch and the auxiliary agent, and carrying out melt extrusion, granulation and drying to obtain PE regenerated plastic particles.
2. The method for preparing PE recycled plastic particles according to claim 1, wherein the compatibilizer is a mixture of maleic anhydride and glycidyl methacrylate in a mass ratio of 3:1.
3. The method for producing PE recycled plastic particles according to claim 1, wherein the initiator is dibenzoyl peroxide or t-butyl hydroperoxide.
4. The method for producing PE recycled plastic particles according to claim 1, wherein the mass ratio of the polyethylene resin, the initiator and the compatibilizer in the first step is 100:2-3:18-20.
5. The method for producing a PE recycled plastic particle according to claim 1, wherein the mass ratio of the polyethylene recovered in the second step, the masterbatch and the auxiliary agent is 100:2-3:4-6.
6. The method for preparing PE recycled plastic particles according to claim 1, wherein the auxiliary agent is prepared by the steps of:
s1, adding 4-hydroxybenzylamine, granular aluminum and triphenoxyaluminum into an autoclave, heating to 150 ℃ and preserving heat for 3 hours, then adding 2-methyl-1-nonene into the autoclave, reacting for 3 hours at 130 ℃, cooling, treating with a small amount of hydrochloric acid, separating liquid, taking an organic phase, adding deionized water, uniformly mixing, extracting with ethyl acetate, taking the organic phase, drying anhydrous magnesium sulfate, filtering, and removing ethyl acetate by rotary evaporation to obtain an intermediate product;
s2, adding DIC, 2-carboxyethyl phenyl hypophosphorous acid and DMF into a three-neck flask with a stirring device, introducing nitrogen for protection, stirring and dissolving uniformly, adding an intermediate product and triethylamine into the system, and heating at room temperature and N 2 Stirring under protection for reaction for 3 hours, after the reaction is finished, distilling under reduced pressure to remove most of solvent DMF, adding deionized water into the product, mixing uniformly, extracting the mixture with toluene, taking an organic layer, drying with anhydrous magnesium sulfate, filtering, and removing toluene by rotary evaporation under reduced pressure to obtain the auxiliary agent.
7. The process for producing PE recycled plastic particles according to claim 6, wherein the amount of 4-hydroxybenzylamine, particulate aluminum, triphenoxyaluminum, 2-methyl-1-nonene used in step S1 is 0.1mol:0.1g:50mg:0.21mol; the ratio of DIC, 2-carboxyethylphenyl hypophosphorous acid, DMF, intermediates and triethylamine used in step S2 was 13.2g:0.105mol:300mL:40.3g:10.1g.
8. The method for producing recycled plastic particles of PE according to claim 6, wherein the triphenoxyaluminum in step S1 is produced by: metallic aluminum is added into phenol, heated to 160 ℃, and reacted for 3 hours to generate triphenoxyaluminum.
9. The process for producing PE recycled plastic particles according to claim 6, wherein the pressure in the autoclave in step S1 is set to 16 to 18kg/cm 2 。
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Effective date of registration: 20231121 Address after: 043600 The First Residential Group of Aili Village, Hengshui Town, Jiang County, Yuncheng City, Shanxi Province Applicant after: Niu Jinfeng Address before: Room 808, 8th floor, Office Building, No. 57 Yingbin Road, Gangcheng Street Street, Haigang District, Qinhuangdao City, Hebei Province, 066000 Applicant before: Hebei Shubang Technology Co.,Ltd. |