CN117659315A - High-strength PE plastic bucket and preparation method thereof - Google Patents
High-strength PE plastic bucket and preparation method thereof Download PDFInfo
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- 229920003023 plastic Polymers 0.000 title claims abstract description 32
- 239000004033 plastic Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000004698 Polyethylene Substances 0.000 claims abstract description 101
- 229920000573 polyethylene Polymers 0.000 claims abstract description 89
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 79
- -1 polyethylene Polymers 0.000 claims abstract description 76
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 39
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 20
- 239000003365 glass fiber Substances 0.000 claims abstract description 12
- 239000000049 pigment Substances 0.000 claims abstract description 12
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005977 Ethylene Substances 0.000 claims abstract description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 46
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 37
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 24
- GNRLUBOJIGSVNT-UHFFFAOYSA-N Aminoethoxyacetic acid Chemical compound NCCOCC(O)=O GNRLUBOJIGSVNT-UHFFFAOYSA-N 0.000 claims description 22
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- VHCOFKDAUBOOTH-UHFFFAOYSA-N ethane pyrrole-2,5-dione Chemical compound CC.C1(C=CC(N1)=O)=O VHCOFKDAUBOOTH-UHFFFAOYSA-N 0.000 claims description 13
- XEDOURVJTJGZAF-UHFFFAOYSA-N 2,6-ditert-butyl-4-prop-2-enylphenol Chemical compound CC(C)(C)C1=CC(CC=C)=CC(C(C)(C)C)=C1O XEDOURVJTJGZAF-UHFFFAOYSA-N 0.000 claims description 11
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 claims description 11
- RIMXEJYJXDBLIE-UHFFFAOYSA-N 6-bromohex-1-ene Chemical compound BrCCCCC=C RIMXEJYJXDBLIE-UHFFFAOYSA-N 0.000 claims description 11
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
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- 238000003756 stirring Methods 0.000 claims description 5
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- 238000005698 Diels-Alder reaction Methods 0.000 abstract description 4
- 150000003254 radicals Chemical class 0.000 abstract description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
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- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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Abstract
The invention discloses a high-strength PE plastic bucket, which is prepared from the following components: 100-120 parts of modified polyethylene, 20-30 parts of reinforcing filler, 3-5 parts of benzoyl peroxide, 20-25 parts of glass fiber and 2-3 parts of pigment. The high-strength PE prepared by the invention utilizes Diels-Alder reaction to generate a cross-linking structure, improves the mechanical property, environmental stress cracking resistance, chemical corrosion resistance and creep resistance of polyethylene, greatly improves the heat resistance of the polyethylene through a thermally reversible covalent bond, also improves the processability of the polyethylene, utilizes free radical reaction to generate a grafting structure of ethylene and reinforcing filler, increases the stability of the reinforcing filler and the polyethylene, and leads the polyethylene to silver-pattern and absorb energy when the nano calcium carbonate in the reinforcing filler is stressed by the outside of the polyethylene, thereby improving the strength of the polyethylene.
Description
Technical Field
The invention relates to the technical field of high-strength PE plastic preparation, in particular to preparation of a high-strength plastic bucket.
Background
Polyethylene (PE), a thermoplastic resin produced by polymerizing ethylene. Industrially, copolymers of ethylene with small amounts of alpha-olefins are also included. Polyethylene is odorless, nontoxic, wax-like in hand feeling, excellent in low temperature resistance (the lowest use temperature can reach-70 to-100 ℃), good in chemical stability, resistant to most of acid and alkali corrosion (acid with oxidation property is not resistant), insoluble in common solvents at normal temperature, small in water absorption, excellent in electrical insulation property, widely applied since commercialization, and first in five general-purpose plastics in yield. The macromolecular chains of polyethylene are in linear or branched structures, crystalline phases and amorphous phases coexist in solid polyethylene, the intermolecular interaction in the amorphous region is weak, and the molecular chains are easy to relatively move under the action of heat and stress, so that the polyethylene has weak heat deformation resistance, low working temperature and poor environmental stress cracking resistance, and cannot meet the use requirements of special environments and special purposes. In order to make up the defects of the polyethylene structure, improve the performance of the polyethylene and expand the application field of the polyethylene, people modify the polyethylene by various physical and chemical modifications, so that the performance of the polyethylene can be improved, the application field is expanded, and different requirements of people on materials are met.
Disclosure of Invention
The invention aims to provide a high-strength PE plastic bucket, which solves the problem of poor strength of the current PE plastic bucket.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the high-strength PE plastic bucket specifically comprises the following steps:
weighing the following raw materials in parts by weight: 100-120 parts of modified polyethylene, 20-30 parts of reinforcing filler, 3-5 parts of benzoyl peroxide, 20-25 parts of glass fiber and 2-3 parts of pigment are added into a single screw extruder, the modified polyethylene, the reinforcing filler and the benzoyl peroxide are premixed for 1-2 hours at the temperature of 200-220 ℃, the glass fiber and the pigment are added, the extruder is cooled and demoulded under the conditions that the temperature of 190-210 ℃ and the rotating speed of 40-50rpm, the rotating speed of a feeder is 4-5rpm, the temperature of a machine head is 185 ℃ and the extruding speed is 600mm/min, and the high-strength PE plastic barrel is prepared.
Further, the modified polyethylene is prepared by the following steps:
step A1: and uniformly mixing furan and tetrahydrofuran, dropwise adding n-butyllithium solution under the condition of nitrogen protection at the rotating speed of 50-70rpm and the temperature of-78 ℃, heating to 25-30 ℃, reacting for 3-5 hours at the rotating speed of 50-70rpm, cooling to-78 ℃, dropwise adding 6-bromo-1-hexene, heating to 25-30 ℃, and reacting for 8-10 hours at the rotating speed of 60-80rpm to obtain the intermediate 1.
Step A2: introducing ethylene gas into a reaction kettle, adding n-hexane, an intermediate 1 and triethylaluminum, activating for 5-10min, uniformly mixing the n-hexane and a Ziegler-Natta catalyst, adding the mixture into the reaction kettle, reacting for 30-50min under the conditions of the rotating speed of 80-100rpm, the temperature of 40-50 ℃ and the pressure of 0.1MPa, adding a mixed solution of hydrochloric acid and ethanol to stop the reaction, obtaining pretreated polyethylene, uniformly mixing the pretreated polyethylene, 1, 2-bis (maleimide) ethane and toluene, reacting for 2-3h under the conditions of the temperature of 80-100 ℃, cooling to 60-70 ℃, and reacting for 22-26h under the conditions of the rotating speed of 80-120rpm, thus obtaining the modified polyethylene.
Further, the dosage ratio of furan, tetrahydrofuran, n-butyllithium solution and 6-bromo-1-hexene described in step A1 was 50mL:12.03g:70mL:32.5g of n-butyllithium solution with a concentration of 1.6mol/L.
Further, the dosage ratio of n-hexane to intermediate 1 in step A2 was 50mL:10g, triethylaluminum in an amount of 1% by mass of intermediate 1, n-hexane and Ziegler-Natta catalyst in an amount ratio of 20mL:1g, hydrochloric acid and ethanol in a molar ratio of 1: the dosage ratio of the modified polyethylene, the 1, 2-bis (maleimide) ethane and the toluene is 1g:0.2g:10mL.
Further, the reinforcing filler is prepared by the following steps:
step B1: uniformly mixing 2- (2-aminoethoxy) acetic acid, trifluoroacetic anhydride, toluene and pyridine, reacting for 30-50min at the speed of 70-80rpm and the temperature of 25-35 ℃, adding 3-butene-1-ol, reacting for 2-3h at the speed of 60-80rpm and the temperature of 80-100 ℃ to obtain intermediate 2, uniformly mixing intermediate 2 and methanol, and continuously introducing ammonia gas at the speed of 50-70rpm and the temperature of 30-40 ℃ to react for 15-30min to obtain intermediate 3.
Step B2: dispersing nano calcium carbonate in ethanol, adding deionized water and KH581 at the rotation speed of 80-100rpm and the temperature of 20-25 ℃, stirring for 30-40min, filtering to remove filtrate, dispersing filter cake in DMF, adding intermediate 3, and photo-curing for 5-10min under the irradiation of 395nm ultraviolet light to obtain the modified nano calcium carbonate.
Step B3: uniformly mixing modified nano calcium carbonate and phosgene solution, reacting for 20-40min at the rotation speed of 60-80rpm and the temperature of 0-10 ℃, continuously introducing phosgene, heating to 50-60 ℃, reacting for 2-3h to obtain modified filler, uniformly mixing the modified filler, 4-allyl-2, 6-di-tert-butylphenol and dibutyltin dilaurate, and reacting for 14-18h at the rotation speed of 80-100rpm and the temperature of 70-90 ℃ under the protection of nitrogen, thereby obtaining the reinforcing filler.
Further, the 2- (2-aminoethoxy) acetic acid, 3-buten-1-ol, trifluoroacetic anhydride and toluene were used in an amount ratio of 1g:0.6g:2.8g:8mL, pyridine amount is 1% of 2- (2-aminoethoxy) acetic acid mass, and mass ratio of intermediate 2 to methanol is 1:2.
further, the dosage ratio of nano calcium carbonate, ethanol, deionized water and KH581 in the step B2 is 1g:5mL:40mL:10mL, filter cake, DMF and intermediate 3 mass ratio of 1:2.8:1.2.
further, the dosage ratio of the modified nano calcium carbonate to the phosgene solution in the step B3 is 1g:10mL of phosgene solution with a concentration of 15% and a mass ratio of the modified monomer to the 4-allyl-2, 6-di-tert-butylphenol ester of 1:2.2 the amount of dibutyltin dilaurate is 2% by mass of 4-allyl-2, 6-di-tert-butylphenol.
The invention has the beneficial effects that:
according to the invention, modified polyethylene and reinforcing monomers are used, polyethylene free radicals and reinforcing monomer free radicals are generated under the initiation of benzoyl peroxide, so that grafting reaction is carried out, the modified polyethylene of the grafting reinforcing monomers is prepared, the modified polyethylene of the grafting reinforcing monomers, glass fibers and pigments are extruded and granulated by a single screw extruder to prepare master batch, the master batch is plasticized and melted, and the master batch is subjected to inflation cooling and de-molding to obtain the high-strength PE plastic barrel.
The modified polyethylene takes furan and 6-bromo-1-hexene as raw materials to prepare an intermediate 1 under the catalysis of n-butyllithium, the intermediate 1 and ethylene gas react under the catalysis of a Ziegler-Natta catalyst to prepare the modified polyethylene with furan rings on side chains, the modified polyethylene further reacts with 1, 2-bis (maleimide) ethane to prepare the modified polyethylene by Diels-Alder reaction, and the crosslinked structure endows the crosslinked polyethylene with thermal reversible crosslinking property, namely covalent bonds generated by Diels-Alder reaction are broken under the high temperature condition, so that the material is de-crosslinked, covalent bonds can be regenerated in the cooling process, and the crosslinked structure is generated again, so that the material can be repeatedly processed and molded for multiple times.
The method comprises the steps of carrying out esterification reaction on 2- (2-aminoethoxy) acetic acid serving as a raw material and 3-butene-1-ol to obtain an intermediate 2, protecting amino groups of the 2- (2-aminoethoxy) acetic acid by using trifluoroacetic anhydride before the reaction, preventing condensation reaction between 2- (2-aminoethoxy) acetic acid monomers, continuously introducing ammonia gas into a solvent serving as a solvent after the intermediate 2 is prepared to remove amino groups of the 2- (2-aminoethoxy) acetic acid from the trifluoroacetic anhydride, carrying out surface treatment on nano calcium carbonate by using KH581, carrying out click reaction on mercapto groups of the modified calcium carbonate and the intermediate 3 under the condition of ultraviolet irradiation to obtain modified nano calcium carbonate, uniformly mixing the modified nano calcium carbonate with phosgene solution, continuously introducing phosgene, converting amino groups on the modified nano calcium carbonate into isocyanato groups, and carrying out reaction on isocyanato groups of the modified monomer and phenol hydroxyl groups of 4-allyl-2, 6-di-tert-butylphenol to obtain the reinforced monomer.
The high-strength PE plastic barrel is prepared by constructing a reticular crosslinked polyethylene system through Diels-Alder reaction, so that the mechanical property, environmental stress cracking resistance, chemical corrosion resistance and creep resistance of the polyethylene are improved, meanwhile, the heat resistance of the polyethylene is greatly improved through a thermally reversible covalent bond, the covalent bond is broken during high-temperature processing, the covalent bond is regenerated during low-temperature processing, the structural stability of the reinforced filler and the polyethylene is improved through grafting of a reinforcing monomer through free radical reaction, the reinforcing monomer takes nano calcium carbonate as a core, silver graining and energy absorption of the polyethylene are caused when the polyethylene is acted by external force, the reinforcing effect is achieved, and the PE plastic barrel has higher strength through interaction of crosslinking and grafting.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments 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
The preparation method of the high-strength PE plastic bucket specifically comprises the following steps:
weighing the following raw materials in parts by weight: 100 parts of modified polyethylene, 20 parts of reinforcing filler, 3 parts of benzoyl peroxide, 20 parts of glass fiber and 2 parts of pigment are added into a single screw extruder, premixed for 1h at the temperature of 200 ℃, glass fiber and pigment are added, and a high-strength PE plastic barrel is prepared by extruding a plastic embryo under the conditions that the temperature of the extruder is 190 ℃, the rotating speed of the extruder is 40rpm, the rotating speed of a feeder is 4rpm, the temperature of a machine head is 185 ℃ and the extruding speed is 600mm/min, and cooling and demolding are carried out.
The modified polyethylene is prepared by the following steps:
step A1: and uniformly mixing furan and tetrahydrofuran, dropwise adding n-butyllithium solution under the condition of nitrogen protection at the rotating speed of 50rpm and the temperature of minus 78 ℃, heating to 25 ℃, reacting for 3 hours at the rotating speed of 50rpm, cooling to the temperature of minus 78 ℃, dropwise adding 6-bromo-1-hexene, heating to 25 ℃, and reacting for 8 hours at the rotating speed of 60rpm to obtain the intermediate 1.
Step A2: introducing ethylene gas into a reaction kettle, adding n-hexane, an intermediate 1 and triethylaluminum, activating for 5min, uniformly mixing the n-hexane and a Ziegler-Natta catalyst, adding the mixture into the reaction kettle, reacting for 30min under the conditions of the rotating speed of 80rpm, the temperature of 40 ℃ and the pressure of 0.1MPa, adding a mixed solution of hydrochloric acid and ethanol to stop the reaction, obtaining pretreated polyethylene, uniformly mixing the pretreated polyethylene, 1, 2-bis (maleimide) ethane and toluene, reacting for 2h under the condition of the temperature of 80 ℃, cooling to 60 ℃, and reacting for 22h under the condition of the rotating speed of 80rpm, thus obtaining the modified polyethylene.
The dosage ratio of furan, tetrahydrofuran, n-butyllithium solution and 6-bromo-1-hexene in step A1 is 50mL:12.03g:70mL:32.5g, n-butyllithium solution at a concentration of 1.6mol/L and furan at 500mL.
The dosage ratio of the n-hexane to the intermediate 1 in the step A2 is 50mL:10g, triethylaluminum in an amount of 1% by mass of intermediate 1, n-hexane and Ziegler-Natta catalyst in an amount ratio of 20mL:1g, hydrochloric acid and ethanol in a molar ratio of 1: the dosage ratio of the modified polyethylene, the 1, 2-bis (maleimide) ethane and the toluene is 1g:0.2g:10mL of n-hexane was used in an amount of 500mL.
The reinforcing filler is prepared by the following steps:
step B1: uniformly mixing 2- (2-aminoethoxy) acetic acid, trifluoroacetic anhydride, toluene and pyridine, reacting for 30min at the speed of 70rpm and the temperature of 25 ℃, adding 3-butene-1-ol, reacting for 2h at the speed of 60rpm and the temperature of 80 ℃ to obtain an intermediate 2, uniformly mixing the intermediate 2 and methanol, continuously introducing ammonia gas at the speed of 50rpm and the temperature of 30 ℃, and reacting for 15min to obtain the intermediate 3.
Step B2: dispersing nano calcium carbonate in ethanol, adding deionized water and KH581 at a rotating speed of 80rpm and a temperature of 20 ℃, stirring for 30min, filtering to remove filtrate, dispersing filter cake in DMF, adding intermediate 3, and photo-curing for 5min under irradiation of 395nm ultraviolet light to obtain the modified nano calcium carbonate.
Step B3: uniformly mixing modified nano calcium carbonate and phosgene solution, reacting for 20min at the rotation speed of 60rpm and the temperature of 0 ℃, continuously introducing phosgene, heating to 50 ℃, reacting for 2h to obtain modified filler, uniformly mixing the modified filler, 4-allyl-2, 6-di-tert-butylphenol and dibutyltin dilaurate, and reacting for 14h at the rotation speed of 80rpm and the temperature of 70 ℃ under the protection of nitrogen to obtain the reinforced filler.
The dosage ratio of 2- (2-aminoethoxy) acetic acid, 3-buten-1-ol, trifluoroacetic anhydride and toluene in step B1 was 1g:0.6g:2.8g:8mL, pyridine amount is 1% of 2- (2-aminoethoxy) acetic acid mass, and mass ratio of intermediate 2 to methanol is 1: the amount of 2,2- (2-aminoethoxy) acetic acid was 815g.
The dosage ratio of the nano calcium carbonate, the ethanol, the deionized water and the KH581 in the step B2 is 1g:5mL:40mL:10mL, filter cake, DMF and intermediate 3 mass ratio of 1:2.8:1.2, the dosage of the nano calcium carbonate is 20g.
The dosage ratio of the modified nano calcium carbonate to the phosgene solution in the step B3 is 1g:10mL of phosgene solution with a concentration of 15% and a mass ratio of the modified monomer to the 4-allyl-2, 6-di-tert-butylphenol ester of 1:2.2, the dosage of the dibutyl tin dilaurate is 2 percent of the mass of the 4-allyl-2, 6-di-tert-butylphenol, and the dosage of the modified nano calcium carbonate is 30g.
Example 2
The preparation method of the high-strength PE plastic bucket specifically comprises the following steps:
weighing the following raw materials in parts by weight: 120 parts of modified polyethylene, 30 parts of reinforcing filler, 5 parts of benzoyl peroxide, 25 parts of glass fiber and 3 parts of pigment are added into a single screw extruder, premixed for 2 hours at 220 ℃, added with the glass fiber and the pigment, extruded into a plastic embryo at the extruder temperature of 210 ℃ and the rotating speed of 50rpm, the rotating speed of a feeder of 5rpm, the temperature of a machine head of 185 ℃ and the extruding speed of 600mm/min, and cooled and demoulded, thus obtaining the high-strength PE plastic barrel.
The modified polyethylene is prepared by the following steps:
step A1: and uniformly mixing furan and tetrahydrofuran, dropwise adding n-butyllithium solution under the condition of nitrogen protection at the rotating speed of 70rpm and the temperature of-78 ℃, heating to 30 ℃, reacting for 5 hours at the rotating speed of 70rpm, cooling to the temperature of-78 ℃, dropwise adding 6-bromo-1-hexene, heating to 30 ℃, and reacting for 10 hours at the rotating speed of 80rpm to obtain the intermediate 1.
Step A2: introducing ethylene gas into a reaction kettle, adding n-hexane, an intermediate 1 and triethylaluminum, activating for 10min, uniformly mixing the n-hexane and a Ziegler-Natta catalyst, adding the mixture into the reaction kettle, reacting for 50min under the conditions of the rotating speed of 100rpm, the temperature of 50 ℃ and the pressure of 0.1MPa, adding a mixed solution of hydrochloric acid and ethanol to stop the reaction, obtaining pretreated polyethylene, uniformly mixing the pretreated polyethylene, 1, 2-bis (maleimide) ethane and toluene, reacting for 3h under the condition of the temperature of 100 ℃, cooling to 70 ℃, and reacting for 26h under the condition of the rotating speed of 120rpm, thus obtaining the modified polyethylene.
The dosage ratio of furan, tetrahydrofuran, n-butyllithium solution and 6-bromo-1-hexene in step A1 is 50mL:12.03g:70mL:32.5g, n-butyllithium solution at a concentration of 1.6mol/L and furan at 500mL.
The dosage ratio of the n-hexane to the intermediate 1 in the step A2 is 50mL:10g, triethylaluminum in an amount of 1% by mass of intermediate 1, n-hexane and Ziegler-Natta catalyst in an amount ratio of 20mL:1g, hydrochloric acid and ethanol in a molar ratio of 1: the dosage ratio of the modified polyethylene, the 1, 2-bis (maleimide) ethane and the toluene is 1g:0.2g:10mL of n-hexane was used in an amount of 500mL.
The reinforcing filler is prepared by the following steps:
step B1: uniformly mixing 2- (2-aminoethoxy) acetic acid, trifluoroacetic anhydride, toluene and pyridine, reacting for 50min at the speed of 80rpm and the temperature of 35 ℃, adding 3-butene-1-ol, reacting for 3h at the speed of 80rpm and the temperature of 100 ℃ to obtain an intermediate 2, uniformly mixing the intermediate 2 and methanol, continuously introducing ammonia gas at the speed of 70rpm and the temperature of 30-40 ℃ to react for 30min to obtain the intermediate 3.
Step B2: dispersing nano calcium carbonate in ethanol, adding deionized water and KH581 at a rotation speed of 100rpm and a temperature of 25 ℃, stirring for 40min, filtering to remove filtrate, dispersing filter cake in DMF, adding intermediate 3, and photo-curing for 10min under irradiation of 395nm ultraviolet light to obtain the modified nano calcium carbonate.
Step B3: uniformly mixing modified nano calcium carbonate and phosgene solution, reacting for 40min at the speed of 80rpm and the temperature of 10 ℃, continuously introducing phosgene, heating to 60 ℃, reacting for 3h to obtain modified filler, uniformly mixing the modified filler, 4-allyl-2, 6-di-tert-butylphenol and dibutyltin dilaurate, and reacting for 18h at the speed of 100rpm and the temperature of 90 ℃ under the protection of nitrogen to obtain the reinforced filler, wherein the dosage of the modified nano calcium carbonate is 30g.
The dosage ratio of 2- (2-aminoethoxy) acetic acid, 3-buten-1-ol, trifluoroacetic anhydride and toluene in step B1 was 1g:0.6g:2.8g:8mL, pyridine amount is 1% of 2- (2-aminoethoxy) acetic acid mass, and mass ratio of intermediate 2 to methanol is 1: the amount of 2,2- (2-aminoethoxy) acetic acid was 815g.
The dosage ratio of the nano calcium carbonate, the ethanol, the deionized water and the KH581 in the step B2 is 1g:5mL:40mL:10mL, filter cake, DMF and intermediate 3 mass ratio of 1:2.8:1.2, the dosage of the nano calcium carbonate is 20g.
The dosage ratio of the modified nano calcium carbonate to the phosgene solution in the step B3 is 1g:10mL of phosgene solution with a concentration of 15% and a mass ratio of the modified monomer to the 4-allyl-2, 6-di-tert-butylphenol ester of 1:2.2 the amount of dibutyltin dilaurate is 2% by mass of 4-allyl-2, 6-di-tert-butylphenol.
Example 3
The preparation method of the high-strength PE plastic bucket specifically comprises the following steps:
weighing the following raw materials in parts by weight: 110 parts of modified polyethylene, 25 parts of reinforcing filler, 4 parts of benzoyl peroxide, 22 parts of glass fiber and 2.5 parts of pigment are added into a single screw extruder, premixed for 1.5 hours at the temperature of 210 ℃, glass fiber and pigment are added, and the high-strength PE plastic barrel is prepared by extruding a blank under the conditions that the temperature of the extruder is 200 ℃, the rotating speed of the extruder is 45rpm, the rotating speed of a feeder is 4rpm, the temperature of a machine head is 185 ℃ and the extruding speed is 600mm/min, and cooling and demoulding.
The modified polyethylene is prepared by the following steps:
step A1: and uniformly mixing furan and tetrahydrofuran, dropwise adding n-butyllithium solution under the condition of nitrogen protection at the rotating speed of 60rpm and the temperature of-78 ℃, heating to 28 ℃, reacting for 4 hours at the rotating speed of 60rpm, cooling to the temperature of-78 ℃, dropwise adding 6-bromo-1-hexene, heating to 28 ℃, and reacting for 9 hours at the rotating speed of 70rpm to obtain the intermediate 1.
Step A2: introducing ethylene gas into a reaction kettle, adding n-hexane, an intermediate 1 and triethylaluminum, activating for 8min, uniformly mixing the n-hexane and a Ziegler-Natta catalyst, adding the mixture into the reaction kettle, reacting for 40min under the conditions of the rotating speed of 90rpm, the temperature of 45 ℃ and the pressure of 0.1MPa, adding a mixed solution of hydrochloric acid and ethanol to stop the reaction, obtaining pretreated polyethylene, uniformly mixing the pretreated polyethylene, 1, 2-bis (maleimide) ethane and toluene, reacting for 2.5h under the condition of the temperature of 90 ℃, cooling to 65 ℃, and reacting for 24h under the condition of the rotating speed of 100rpm, thus obtaining the modified polyethylene.
The dosage ratio of furan, tetrahydrofuran, n-butyllithium solution and 6-bromo-1-hexene in step A1 is 50mL:12.03g:70mL:32.5g, n-butyllithium solution at a concentration of 1.6mol/L and furan at 500mL.
The dosage ratio of the n-hexane to the intermediate 1 in the step A2 is 50mL:10g, triethylaluminum in an amount of 1% by mass of intermediate 1, n-hexane and Ziegler-Natta catalyst in an amount ratio of 20mL:1g, hydrochloric acid and ethanol in a molar ratio of 1: the dosage ratio of the modified polyethylene, the 1, 2-bis (maleimide) ethane and the toluene is 1g:0.2g:10mL of n-hexane was used in an amount of 500mL.
The reinforcing filler is prepared by the following steps:
step B1: uniformly mixing 2- (2-aminoethoxy) acetic acid, trifluoroacetic anhydride, toluene and pyridine, reacting for 40min at the speed of 75rpm and the temperature of 30 ℃, adding 3-butene-1-ol, reacting for 2.5h at the speed of 70rpm and the temperature of 90 ℃ to obtain an intermediate 2, uniformly mixing the intermediate 2 and methanol, continuously introducing ammonia gas at the speed of 60rpm and the temperature of 35 ℃ to react for 22min to obtain the intermediate 3.
Step B2: dispersing nano calcium carbonate in ethanol, adding deionized water and KH581 at a rotation speed of 90rpm and a temperature of 22 ℃, stirring for 35min, filtering to remove filtrate, dispersing filter cake in DMF, adding intermediate 3, and photo-curing for 8min under irradiation of 395nm ultraviolet light to obtain the modified nano calcium carbonate.
Step B3: uniformly mixing modified nano calcium carbonate and phosgene solution, reacting for 30min at the speed of 70rpm and the temperature of 5 ℃, continuously introducing phosgene, heating to 55 ℃, reacting for 2.5h to obtain modified filler, uniformly mixing the modified filler, 4-allyl-2, 6-di-tert-butylphenol and dibutyltin dilaurate, and reacting for 16h at the speed of 90rpm and the temperature of 80 ℃ under the protection of nitrogen to obtain the reinforced filler.
The dosage ratio of 2- (2-aminoethoxy) acetic acid, 3-buten-1-ol, trifluoroacetic anhydride and toluene in step B1 was 1g:0.6g:2.8g:8mL, pyridine amount is 1% of 2- (2-aminoethoxy) acetic acid mass, and mass ratio of intermediate 2 to methanol is 1: the amount of 2,2- (2-aminoethoxy) acetic acid was 815g.
The dosage ratio of the nano calcium carbonate, the ethanol, the deionized water and the KH581 in the step B2 is 1g:5mL:40mL:10mL, filter cake, DMF and intermediate 3 mass ratio of 1:2.8:1.2, the dosage of the nano calcium carbonate is 20g.
The dosage ratio of the modified nano calcium carbonate to the phosgene solution in the step B3 is 1g:10mL of phosgene solution with a concentration of 15% and a mass ratio of the modified monomer to the 4-allyl-2, 6-di-tert-butylphenol ester of 1:2.2, the dosage of the dibutyl tin dilaurate is 2 percent of the mass of the 4-allyl-2, 6-di-tert-butylphenol, and the dosage of the modified nano calcium carbonate is 30g.
Comparative example 1:
this comparative example was carried out in the same manner as in example 1 except that 1, 2-bis (maleimide) ethane was not added.
Comparative example 2:
this comparative example uses modified nano calcium carbonate instead of reinforcing filler as compared to example 1, the rest of the procedure being the same.
Comparative example 3:
in this comparative example, polyethylene 20000 was used instead of the modified polyethylene as in example 1, and the rest of the procedure was the same.
The high strength PE composites prepared in examples 1-3 and comparative examples 1-3 were prepared according to I SO 527-1:2012, testing tensile yield stress according to GB/T1040.2-2006, and testing notched impact strength of a simply supported beam according to GB/T1043.1-2008.
The test results were as follows:
as is clear from the above table, the high-strength PE materials prepared in examples 1 to 3 have more excellent physical properties than those of comparative examples 1 to 3, and the comparative example 1 has no net-shaped cross-linked structure due to the fact that no 1, 2-bis (maleimide) ethane is added, so that the tensile yield stress and the notched impact strength of the simply supported beams of polyethylene are reduced, the comparative example 2 uses modified nano calcium carbonate instead of reinforcing filler, grafting with polyethylene is not performed in the melting process, but simple blending, so that the tensile yield stress and the notched impact strength of polyethylene are reduced, the comparative example 3 uses polyethylene 20000 instead of modified polyethylene, the cross-linked structure is absent in comparison example 1, and the polar groups of side chains are absent in comparison example 1, so that the tensile yield stress and the notched impact strength of the simply supported beams of polyethylene are lower than those of example 1, and the high-strength PE prepared in the invention has good physical properties, and can be applied to plastic barrels in a better manner.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (9)
1. A preparation method of a high-strength PE plastic bucket is characterized by comprising the following steps: the method specifically comprises the following steps:
weighing the following raw materials in parts by weight: 100-120 parts of modified polyethylene, 20-30 parts of reinforcing filler, 3-5 parts of benzoyl peroxide, 20-30 parts of glass fiber and 2-3 parts of pigment, adding the modified polyethylene, the reinforcing filler and the benzoyl peroxide into a single screw extruder for premixing, adding the glass fiber and the pigment, extruding the embryo, cooling and demoulding to obtain the high-strength PE plastic barrel.
2. The method for preparing the high-strength PE plastic bucket according to claim 1, wherein the method comprises the following steps: the modified polyethylene is prepared by the following steps:
step A1: uniformly mixing furan and tetrahydrofuran, dropwise adding n-butyllithium solution, heating to react, cooling, dropwise adding 6-bromo-1-hexene, heating to react, and obtaining an intermediate 1;
step A2: introducing ethylene gas into a reaction kettle, adding n-hexane, an intermediate 1 and triethylaluminum for activation, uniformly mixing the n-hexane and a Ziegler-Natta catalyst, adding the mixture into the reaction kettle for reaction to obtain pretreated polyethylene, uniformly mixing the pretreated polyethylene, 1, 2-bis (maleimide) ethane and toluene, and reacting to obtain the modified polyethylene.
3. The method for preparing the high-strength PE plastic bucket according to claim 2, wherein the method comprises the following steps:
the dosage ratio of furan, tetrahydrofuran, n-butyllithium solution and 6-bromo-1-hexene in step A1 is 50mL:12.03g:70mL:32.5g of n-butyllithium solution with a concentration of 1.6mol/L.
4. The method for preparing the high-strength PE plastic bucket according to claim 2, wherein the method comprises the following steps:
the dosage ratio of the n-hexane to the intermediate 1 in the step A2 is 50mL:10g, triethylaluminum in an amount of 1% by mass of intermediate 1, n-hexane and Ziegler-Natta catalyst in an amount ratio of 20mL:1g, hydrochloric acid and ethanol in a molar ratio of 1: the dosage ratio of the modified polyethylene, the 1, 2-bis (maleimide) ethane and the toluene is 1g:0.2g:10mL.
5. The method for preparing the high-strength PE plastic bucket according to claim 1, wherein the method comprises the following steps: the reinforcing filler is prepared by the following steps:
step B1: uniformly mixing 2- (2-aminoethoxy) acetic acid, trifluoroacetic anhydride, toluene and pyridine, adding 3-butene-1-ol to obtain an intermediate 2, uniformly mixing the intermediate 2 and methanol, continuously introducing ammonia gas, and reacting to obtain an intermediate 3;
step B2: dispersing nano calcium carbonate in ethanol, adding deionized water and KH581, stirring and filtering, removing filtrate, dispersing filter cake in DMF, adding intermediate 3, and photo-curing under ultraviolet irradiation to obtain modified nano calcium carbonate;
step B3: uniformly mixing modified nano calcium carbonate and phosgene solution, continuously introducing phosgene and heating to prepare modified filler, and uniformly mixing the modified filler, 4-allyl-2, 6-di-tert-butylphenol and dibutyltin dilaurate to prepare the reinforcing filler.
6. The method for preparing the high-strength PE plastic bucket according to claim 5, wherein the method comprises the following steps:
the dosage ratio of 2- (2-aminoethoxy) acetic acid, 3-buten-1-ol, trifluoroacetic anhydride and toluene in step B1 was 1g:0.6g:2.8g:8mL, pyridine amount is 1% of 2- (2-aminoethoxy) acetic acid mass, and mass ratio of intermediate 2 to methanol is 1:2.
7. the method for preparing the high-strength PE plastic bucket according to claim 5, wherein the method comprises the following steps:
the dosage ratio of the nano calcium carbonate, the ethanol, the deionized water and the KH581 in the step B2 is 1g:5mL:40mL:10mL, filter cake, DMF and intermediate 3 mass ratio of 1:2.8:1.2.
8. the method for preparing the high-strength PE plastic bucket according to claim 5, wherein the method comprises the following steps:
the dosage ratio of the modified nano calcium carbonate to the phosgene solution in the step B3 is 1g:10mL of phosgene solution with a concentration of 15% and a mass ratio of the modified monomer to the 4-allyl-2, 6-di-tert-butylphenol ester of 1:2.2 the amount of dibutyltin dilaurate is 2% by mass of 4-allyl-2, 6-di-tert-butylphenol.
9. A high strength PE plastic drum, its characterized in that: the preparation method according to any one of claims 1-8.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4390666A (en) * | 1981-08-14 | 1983-06-28 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyethylene blend composition |
| JP2012201812A (en) * | 2011-03-25 | 2012-10-22 | Umg Abs Ltd | Reinforced thermoplastic resin composition |
| CN113429730A (en) * | 2021-07-16 | 2021-09-24 | 安庆市悦发管业有限公司 | High-strength high-temperature-resistant water supply pipe and preparation method thereof |
| CN114410035A (en) * | 2022-03-16 | 2022-04-29 | 图方便（苏州）环保科技有限公司 | Anti-aging flame-retardant pipeline material and preparation method thereof |
| CN117164977A (en) * | 2023-09-06 | 2023-12-05 | 广东定通实业有限公司 | PE composite plastic and preparation method thereof |
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2023
- 2023-12-21 CN CN202311772472.4A patent/CN117659315A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4390666A (en) * | 1981-08-14 | 1983-06-28 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyethylene blend composition |
| JP2012201812A (en) * | 2011-03-25 | 2012-10-22 | Umg Abs Ltd | Reinforced thermoplastic resin composition |
| CN113429730A (en) * | 2021-07-16 | 2021-09-24 | 安庆市悦发管业有限公司 | High-strength high-temperature-resistant water supply pipe and preparation method thereof |
| CN114410035A (en) * | 2022-03-16 | 2022-04-29 | 图方便（苏州）环保科技有限公司 | Anti-aging flame-retardant pipeline material and preparation method thereof |
| CN117164977A (en) * | 2023-09-06 | 2023-12-05 | 广东定通实业有限公司 | PE composite plastic and preparation method thereof |
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