CN118496608B - High temperature resistant fluoroelastomer processing aid for slurry polyethylene process and preparation method thereof - Google Patents
High temperature resistant fluoroelastomer processing aid for slurry polyethylene process and preparation method thereof Download PDFInfo
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- CN118496608B CN118496608B CN202410723441.8A CN202410723441A CN118496608B CN 118496608 B CN118496608 B CN 118496608B CN 202410723441 A CN202410723441 A CN 202410723441A CN 118496608 B CN118496608 B CN 118496608B
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- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 31
- 239000006057 Non-nutritive feed additive Substances 0.000 title claims abstract description 30
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 28
- -1 polyethylene Polymers 0.000 title claims abstract description 28
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002002 slurry Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 64
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 24
- 239000011737 fluorine Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 28
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 28
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 21
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 17
- GVHVFKOKIKGZTR-UHFFFAOYSA-N 2,3,4-trifluoro-6-methylaniline Chemical compound CC1=CC(F)=C(F)C(F)=C1N GVHVFKOKIKGZTR-UHFFFAOYSA-N 0.000 claims description 14
- FTZQXOJYPFINKJ-UHFFFAOYSA-N 2-fluoroaniline Chemical compound NC1=CC=CC=C1F FTZQXOJYPFINKJ-UHFFFAOYSA-N 0.000 claims description 14
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 14
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 244000028419 Styrax benzoin Species 0.000 claims description 14
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 14
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 14
- 229960002130 benzoin Drugs 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 235000019382 gum benzoic Nutrition 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 238000007363 ring formation reaction Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 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 7
- 239000003063 flame retardant Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 241000251730 Chondrichthyes Species 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000005461 lubrication Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000007613 slurry method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004614 Process Aid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007493 shaping process 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
本发明涉及氟弹性体加工助剂技术领域，且公开了一种用于淤浆法聚乙烯工艺耐高温氟弹性体加工助剂及制备方法，本发明通过将氧化石墨烯改性环氧树脂、含氟修饰环氧树脂、四氟乙烯‑偏氟乙烯共聚物加入双螺旋挤出机中，挤出，将挤出物进行粉碎，丙酮提取，过滤、干燥，得到用于淤浆法聚乙烯工艺耐高温氟弹性体加工助剂；其中的环氧树脂具有较好的耐温性，氧化石墨烯具有较好的润滑效果，使得模头的孔口处不会产生堵塞，其中通过接枝含有的大量的氟化物，应用在聚乙烯中也可以减少树脂之间的摩擦，推迟鲨鱼皮熔体破裂，使其表面更光滑，同时提高了加工性能和材料流动速率；其中氧化石墨烯本身就具有较好的阻燃效果和助剂中是硫元素协效阻燃。The invention relates to the technical field of fluoroelastomer processing aids, and discloses a high-temperature resistant fluoroelastomer processing aid for a slurry polyethylene process and a preparation method thereof. The invention provides a high-temperature resistant fluoroelastomer processing aid for a slurry polyethylene process by adding graphene oxide modified epoxy resin, fluorine-containing modified epoxy resin and tetrafluoroethylene-vinylidene fluoride copolymer into a double screw extruder, extruding, crushing the extrudate, extracting with acetone, filtering and drying. The high-temperature resistant fluoroelastomer processing aid for a slurry polyethylene process is obtained. The epoxy resin has good temperature resistance, and the graphene oxide has good lubrication effect, so that the orifice of the die head will not be blocked. A large amount of fluoride contained by grafting can be applied to polyethylene to reduce friction between resins, delay shark skin melt fracture, make the surface smoother, and improve processing performance and material flow rate. The graphene oxide itself has good flame retardant effect, and the sulfur element in the additive is synergistic flame retardant.
Description
Technical Field
The invention relates to the technical field of fluoroelastomer processing aids, in particular to a high-temperature-resistant fluoroelastomer processing aid for a slurry polyethylene process and a preparation method thereof.
Background
The low pressure slurry polyethylene process is a slurry loop and gas phase fluidized bed series process, having two reactors in series, with the capability of producing bimodal polyethylene, the first reactor being a loop slurry reactor followed by a gas phase fluidized bed reactor, and often causing a blockage at the die during extrusion and shaping production processes, resulting in reduced product quality and efficiency and melt fracture. The graphene oxide has better lubricating property and flame retardant property, so that the graphene oxide is inspired to react with epoxy resin and fluorine-containing compound to prepare the fluoroelastomer processing aid with excellent performance.
Disclosure of Invention
(One) solving the technical problems
Aiming at the defects of the prior art, the invention provides a high-temperature-resistant fluoroelastomer processing aid for a slurry polyethylene process and a preparation method thereof, which are used for improving melt fracture, improving processing performance, improving material flow rate and simultaneously having better flame retardant effect.
(II) technical scheme
The invention provides a high-temperature resistant fluoroelastomer processing aid for a slurry polyethylene process, which comprises, by weight, 4-8 parts of graphene oxide modified epoxy resin, 10-25 parts of fluorine-containing modified epoxy resin and 40-60 parts of tetrafluoroethylene-vinylidene fluoride copolymer.
Preferably, the preparation method of the graphene oxide modified epoxy resin comprises the following steps:
s1, adding the water-based epoxy resin and the ethylenediamine curing agent into a reactor, stirring at a high speed, adding graphene oxide into the reactor, and performing ultrasonic treatment for 40-70min to obtain the graphene oxide modified epoxy resin.
Preferably, the mass ratio of the aqueous epoxy resin to the ethylenediamine curing agent to the graphene oxide is 1:0.02-0.04:1.1-1.3.
Preferably, the preparation method of the fluorine-containing modified epoxy resin comprises the following steps:
(1) Adding p-hydroxybenzaldehyde and o-aminotrifluorotoluene into an N, N-dimethylformamide solvent, reacting for 8-12h at 75-90 ℃, distilling under reduced pressure after the reaction is finished, filtering and drying to obtain an intermediate 1;
(2) Adding an intermediate 1 and 4-amino-3-fluorobenzene mercaptan into an N, N-dimethylformamide solvent, uniformly stirring, then adding a benzoin dimethyl ether photoinitiator, irradiating with 365nm ultraviolet light for 2-4h at 40-50 ℃, centrifuging, washing with distilled water, and drying to obtain an intermediate 2;
(3) Adding an intermediate 2, polyethylene glycol and epichlorohydrin into a tetrahydrofuran solvent, stirring and dissolving, then continuously adding a boron trifluoride diethyl etherate catalyst, reacting for 2-4 hours at 20-25 ℃, then continuously adding sodium hydroxide into the mixture for ring closure reaction, heating to 60-70 ℃ for reacting for 3-4 hours, centrifuging and separating after the completion, and washing with n-hexane for 2-3 times to obtain the fluorine-containing modified epoxy resin.
Preferably, the mass ratio of the parahydroxybenzaldehyde to the o-aminotrifluorotoluene in the step (1) is 1:1.1-1.3.
Preferably, the mass ratio of the intermediate 1, 4-amino-3-fluorobenzene mercaptan to benzoin dimethyl ether photoinitiator in the step (2) is 1.2-1.3:1:0.02-0.03.
Preferably, the mass ratio of the intermediate 2, the polyethylene glycol, the epichlorohydrin, the boron trifluoride diethyl ether catalyst and the sodium hydroxide in the step (3) is 0.8-1.2:1:2.8-3.5:0.04-0.06:0.05-0.07.
Preferably, the preparation method of the high-temperature-resistant fluoroelastomer processing aid for the slurry method polyethylene process comprises the steps of adding graphene oxide modified epoxy resin, fluorine-containing modified epoxy resin and tetrafluoroethylene-vinylidene fluoride copolymer into a double-screw extruder, extruding at 170-180 ℃ for 50-60min, crushing the extrudate, extracting with acetone for 6-9h, filtering and drying to obtain the high-temperature-resistant fluoroelastomer processing aid for the slurry method polyethylene process.
(III) beneficial technical effects
According to the invention, graphene oxide modified epoxy resin, fluorine-containing modified epoxy resin and tetrafluoroethylene-vinylidene fluoride copolymer are added into a double-screw extruder to be extruded, the extrudate is crushed, acetone is extracted, and the high-temperature-resistant fluoroelastomer processing aid for a slurry polyethylene process is obtained after filtration and drying.
The graphene oxide modified epoxy resin and the fluorine-containing modified epoxy resin have epoxy resin structures, so that the graphene oxide modified epoxy resin and the fluorine-containing modified epoxy resin have good compatibility, the dispersibility in a high-temperature-resistant fluoroelastomer processing aid for a slurry polyethylene process is improved, the epoxy resin has good temperature resistance, the graphene oxide has good lubricating effect, the orifice of a die head cannot be blocked, a large amount of fluoride contained by grafting is used in the polyethylene, friction among the resins can be reduced, melt fracture of shark skin is delayed, the surface of the shark skin is smoother, the processing performance and the material flow rate are improved, and the graphene oxide has good flame retardant effect and sulfur element synergistic flame retardant in the aid.
Detailed Description
Example 1
(1) Adding parahydroxybenzaldehyde and o-aminotrifluorotoluene into an N, N-dimethylformamide solvent, wherein the mass ratio of the parahydroxybenzaldehyde to the o-aminotrifluorotoluene is 1:1.1, reacting for 8 hours at 75 ℃, decompressing and distilling after finishing, filtering and drying to obtain an intermediate 1;
(2) Adding an intermediate 1 and 4-amino-3-fluorobenzene mercaptan into an N, N-dimethylformamide solvent, uniformly stirring, then adding a benzoin dimethyl ether photoinitiator into the mixture, wherein the mass ratio of the intermediate 1 to the 4-amino-3-fluorobenzene mercaptan to the benzoin dimethyl ether photoinitiator is 1.2:1:0.02, irradiating 365nm ultraviolet light for 2 hours at 40 ℃, centrifuging, washing with distilled water, and drying to obtain an intermediate 2;
(3) Adding an intermediate 2, polyethylene glycol and epichlorohydrin into a tetrahydrofuran solvent, stirring and dissolving, then continuously adding a boron trifluoride diethyl ether catalyst, reacting for 2 hours at 20 ℃, then continuously adding sodium hydroxide into the mixture for ring-closure reaction, wherein the mass ratio of the intermediate 2 to the polyethylene glycol to the epichlorohydrin to the boron trifluoride diethyl ether catalyst to the sodium hydroxide is 0.8:1:2.8:0.04:0.05, heating the mixture to 60 ℃ for reacting for 3 hours, centrifuging the mixture after the reaction is finished, and washing the mixture with n-hexane for 2 times to obtain fluorine-containing modified epoxy resin;
(4) Adding the aqueous epoxy resin and the ethylenediamine curing agent into a reactor, stirring at a high speed, and then adding graphene oxide into the reactor, wherein the mass ratio of the aqueous epoxy resin to the ethylenediamine curing agent to the graphene oxide is 1:0.02:1.1, and performing ultrasonic treatment for 40min to obtain graphene oxide modified epoxy resin;
(5) Adding 4 parts by weight of graphene oxide modified epoxy resin, 10 parts by weight of fluorine-containing modified epoxy resin and 40 parts by weight of tetrafluoroethylene-vinylidene fluoride copolymer into a double-screw extruder, extruding at 170 ℃ for 50min, crushing the extrudate, extracting with acetone for 6h, filtering and drying to obtain the high-temperature-resistant fluoroelastomer processing aid for the slurry polyethylene process.
Example 2
(1) Adding p-hydroxybenzaldehyde and o-aminotrifluorotoluene into an N, N-dimethylformamide solvent, wherein the mass ratio of the p-hydroxybenzaldehyde to the o-aminotrifluorotoluene is 1:1.3, reacting for 12 hours at 90 ℃, decompressing and distilling after the reaction is finished, filtering and drying to obtain an intermediate 1;
(2) Adding an intermediate 1 and 4-amino-3-fluorobenzene mercaptan into an N, N-dimethylformamide solvent, uniformly stirring, then adding a benzoin dimethyl ether photoinitiator into the mixture, wherein the mass ratio of the intermediate 1 to the 4-amino-3-fluorobenzene mercaptan to the benzoin dimethyl ether photoinitiator is 1.3:1:0.03, irradiating 365nm ultraviolet light for 4 hours at 50 ℃, centrifuging, washing with distilled water, and drying to obtain an intermediate 2;
(3) Adding an intermediate 2, polyethylene glycol and epichlorohydrin into a tetrahydrofuran solvent, stirring and dissolving, then continuously adding a boron trifluoride diethyl ether catalyst, reacting for 4 hours at 25 ℃, then continuously adding sodium hydroxide into the mixture for ring-closure reaction, wherein the mass ratio of the intermediate 2 to the polyethylene glycol to the epichlorohydrin to the boron trifluoride diethyl ether catalyst to the sodium hydroxide is 1.2:1:3.5:0.06:0.07, heating to 70 ℃ for reacting for 4 hours, centrifuging after the reaction is finished, and washing with n-hexane for 3 times to obtain fluorine-containing modified epoxy resin;
(4) Adding the aqueous epoxy resin and the ethylenediamine curing agent into a reactor, stirring at a high speed, and then adding graphene oxide into the reactor, wherein the mass ratio of the aqueous epoxy resin to the ethylenediamine curing agent to the graphene oxide is 1:0.04:1.3, and performing ultrasonic treatment for 70min to obtain graphene oxide modified epoxy resin;
(5) Adding 8 parts by weight of graphene oxide modified epoxy resin, 25 parts by weight of fluorine-containing modified epoxy resin and 60 parts by weight of tetrafluoroethylene-vinylidene fluoride copolymer into a double-screw extruder, extruding at 180 ℃ for 60min, crushing the extrudate, extracting with acetone for 9h, filtering and drying to obtain the high-temperature-resistant fluoroelastomer processing aid for the slurry polyethylene process.
Example 3
(1) Adding p-hydroxybenzaldehyde and o-aminotrifluorotoluene into an N, N-dimethylformamide solvent, wherein the mass ratio of the p-hydroxybenzaldehyde to the o-aminotrifluorotoluene is 1:1.2, reacting for 10 hours at 82.5 ℃, and after the reaction, distilling under reduced pressure, filtering and drying to obtain an intermediate 1;
(2) Adding an intermediate 1 and 4-amino-3-fluorobenzene mercaptan into an N, N-dimethylformamide solvent, uniformly stirring, then adding a benzoin dimethyl ether photoinitiator, wherein the mass ratio of the intermediate 1 to the 4-amino-3-fluorobenzene mercaptan to the benzoin dimethyl ether photoinitiator is 1.25:1:0.025, irradiating 365nm ultraviolet light for 3 hours at 45 ℃, centrifuging, washing with distilled water, and drying to obtain an intermediate 2;
(3) Adding an intermediate 2, polyethylene glycol and epichlorohydrin into a tetrahydrofuran solvent, stirring and dissolving, then continuously adding a boron trifluoride diethyl ether catalyst, reacting for 3 hours at 22.5 ℃, then continuously adding sodium hydroxide into the mixture for ring closure reaction, wherein the mass ratio of the intermediate 2 to the polyethylene glycol to the epichlorohydrin to the boron trifluoride diethyl ether catalyst to the sodium hydroxide is 1.0:1:3.15:0.05:0.06, heating to 65 ℃ for reacting for 3.5 hours, centrifuging and separating after the reaction is finished, and washing n-hexane for 2.5 times to obtain fluorine-containing modified epoxy resin;
(4) Adding the aqueous epoxy resin and the ethylenediamine curing agent into a reactor, stirring at a high speed, and then adding graphene oxide into the reactor, wherein the mass ratio of the aqueous epoxy resin to the ethylenediamine curing agent to the graphene oxide is 1:0.03:1.2, and performing ultrasonic treatment for 55min to obtain graphene oxide modified epoxy resin;
(5) Adding 6 parts by weight of graphene oxide modified epoxy resin, 17.5 parts by weight of fluorine-containing modified epoxy resin and 50 parts by weight of tetrafluoroethylene-vinylidene fluoride copolymer into a double-screw extruder, extruding at 175 ℃ for 55min, crushing the extrudate, extracting with acetone for 7.5h, filtering and drying to obtain the high-temperature-resistant fluoroelastomer processing aid for the slurry polyethylene process.
Example 4
(1) Adding parahydroxybenzaldehyde and o-aminotrifluorotoluene into an N, N-dimethylformamide solvent, wherein the mass ratio of the parahydroxybenzaldehyde to the o-aminotrifluorotoluene is 1:1.1, reacting for 8 hours at 75 ℃, decompressing and distilling after finishing, filtering and drying to obtain an intermediate 1;
(2) Adding an intermediate 1 and 4-amino-3-fluorobenzene mercaptan into an N, N-dimethylformamide solvent, uniformly stirring, then adding a benzoin dimethyl ether photoinitiator into the mixture, wherein the mass ratio of the intermediate 1 to the 4-amino-3-fluorobenzene mercaptan to the benzoin dimethyl ether photoinitiator is 1.2:1:0.02, irradiating 365nm ultraviolet light for 2 hours at 40 ℃, centrifuging, washing with distilled water, and drying to obtain an intermediate 2;
(3) Adding an intermediate 2, polyethylene glycol and epichlorohydrin into a tetrahydrofuran solvent, stirring and dissolving, then continuously adding a boron trifluoride diethyl ether catalyst, reacting for 4 hours at 25 ℃, then continuously adding sodium hydroxide into the mixture for ring-closure reaction, wherein the mass ratio of the intermediate 2 to the polyethylene glycol to the epichlorohydrin to the boron trifluoride diethyl ether catalyst to the sodium hydroxide is 1.2:1:3.5:0.06:0.07, heating to 70 ℃ for reacting for 4 hours, centrifuging after the reaction is finished, and washing with n-hexane for 3 times to obtain fluorine-containing modified epoxy resin;
(4) Adding the aqueous epoxy resin and the ethylenediamine curing agent into a reactor, stirring at a high speed, and then adding graphene oxide into the reactor, wherein the mass ratio of the aqueous epoxy resin to the ethylenediamine curing agent to the graphene oxide is 1:0.04:1.3, and performing ultrasonic treatment for 70min to obtain graphene oxide modified epoxy resin;
(5) Adding 6 parts by weight of graphene oxide modified epoxy resin, 17.5 parts by weight of fluorine-containing modified epoxy resin and 50 parts by weight of tetrafluoroethylene-vinylidene fluoride copolymer into a double-screw extruder, extruding at 175 ℃ for 55min, crushing the extrudate, extracting with acetone for 7.5h, filtering and drying to obtain the high-temperature-resistant fluoroelastomer processing aid for the slurry polyethylene process.
Example 5
(1) Adding p-hydroxybenzaldehyde and o-aminotrifluorotoluene into an N, N-dimethylformamide solvent, wherein the mass ratio of the p-hydroxybenzaldehyde to the o-aminotrifluorotoluene is 1:1.3, reacting for 12 hours at 90 ℃, decompressing and distilling after the reaction is finished, filtering and drying to obtain an intermediate 1;
(2) Adding an intermediate 1 and 4-amino-3-fluorobenzene mercaptan into an N, N-dimethylformamide solvent, uniformly stirring, then adding a benzoin dimethyl ether photoinitiator into the mixture, wherein the mass ratio of the intermediate 1 to the 4-amino-3-fluorobenzene mercaptan to the benzoin dimethyl ether photoinitiator is 1.3:1:0.03, irradiating 365nm ultraviolet light for 4 hours at 50 ℃, centrifuging, washing with distilled water, and drying to obtain an intermediate 2;
(3) Adding an intermediate 2, polyethylene glycol and epichlorohydrin into a tetrahydrofuran solvent, stirring and dissolving, then continuously adding a boron trifluoride diethyl ether catalyst, reacting for 3 hours at 22.5 ℃, then continuously adding sodium hydroxide into the mixture for ring closure reaction, wherein the mass ratio of the intermediate 2 to the polyethylene glycol to the epichlorohydrin to the boron trifluoride diethyl ether catalyst to the sodium hydroxide is 1.0:1:3.15:0.05:0.06, heating to 65 ℃ for reacting for 3.5 hours, centrifuging and separating after the reaction is finished, and washing n-hexane for 2.5 times to obtain fluorine-containing modified epoxy resin;
(4) Adding the aqueous epoxy resin and the ethylenediamine curing agent into a reactor, stirring at a high speed, and then adding graphene oxide into the reactor, wherein the mass ratio of the aqueous epoxy resin to the ethylenediamine curing agent to the graphene oxide is 1:0.03:1.2, and performing ultrasonic treatment for 55min to obtain graphene oxide modified epoxy resin;
(5) Adding 4 parts by weight of graphene oxide modified epoxy resin, 10 parts by weight of fluorine-containing modified epoxy resin and 40 parts by weight of tetrafluoroethylene-vinylidene fluoride copolymer into a double-screw extruder, extruding at 170 ℃ for 50min, crushing the extrudate, extracting with acetone for 6h, filtering and drying to obtain the high-temperature-resistant fluoroelastomer processing aid for the slurry polyethylene process.
Comparative example 1
In this comparative example, no graphene oxide-modified epoxy resin was added as compared with example 5.
Comparative example 2
In this comparative example, no fluorine-containing modified epoxy resin was added as compared with example 5.
The fluoroelastomer process aid of examples 1-5 and comparative examples 1-2 were mixed with polyethylene and extrusion tested on a haak rheometer for extrusion time and extrusion torque, head pressure, melt fracture test results are shown in table 1.
TABLE 1 fluoroelastomer processing aid performance test.
As can be seen from Table 1, the fluoroelastomer processing aids prepared in examples 1-5 of the present invention have reduced melt fracture elimination time and more head pressure and torque reduction than the fluoroelastomer processing aids prepared in comparative examples 1-2, indicating better flow rates, improved melt fracture and improved processability.
The limiting oxygen index of the material was measured using an oxygen index meter and the combustion grade of the mixed material was measured using a horizontal vertical burner with fluoroelastomer processing aid and polyethylene.
TABLE 2 flame retardancy test.
| Project | Limiting oxygen index (%) | Combustion grade |
| Example 1 | 28 | V-0 |
| Example 2 | 35 | V-0 |
| Example 3 | 33 | V-0 |
| Example 4 | 29 | V-0 |
| Example 5 | 30 | V-0 |
| Comparative example 1 | 24 | V-1 |
| Comparative example 2 | 21 | V-1 |
As can be seen from Table 2, the fluoroelastomer processing aid prepared in examples 1-5 of the present invention was applied to polyethylene to provide a better flame retardant effect than the fluoroelastomer processing aid prepared in comparative examples 1-2.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (2)
1. A high-temperature resistant fluoroelastomer processing aid for a slurry polyethylene process is characterized by comprising, by weight, 4-8 parts of graphene oxide modified epoxy resin, 10-25 parts of fluorine-containing modified epoxy resin and 40-60 parts of tetrafluoroethylene-vinylidene fluoride copolymer;
the preparation method of the graphene oxide modified epoxy resin is characterized by comprising the following steps:
S1, adding aqueous epoxy resin and an ethylenediamine curing agent into a reactor, stirring at a high speed, adding graphene oxide into the reactor, and performing ultrasonic treatment for 40-70min to obtain graphene oxide modified epoxy resin;
The mass ratio of the aqueous epoxy resin to the ethylenediamine curing agent to the graphene oxide is 1:0.02-0.04:1.1-1.3;
the preparation method of the fluorine-containing modified epoxy resin comprises the following steps:
(1) Adding p-hydroxybenzaldehyde and o-aminotrifluorotoluene into an N, N-dimethylformamide solvent, reacting for 8-12h at 75-90 ℃, distilling under reduced pressure after the reaction is finished, filtering and drying to obtain an intermediate 1;
(2) Adding an intermediate 1 and 4-amino-3-fluorobenzene mercaptan into an N, N-dimethylformamide solvent, uniformly stirring, then adding a benzoin dimethyl ether photoinitiator, irradiating with 365nm ultraviolet light for 2-4h at 40-50 ℃, centrifuging, washing with distilled water, and drying to obtain an intermediate 2;
(3) Adding an intermediate 2, polyethylene glycol and epichlorohydrin into a tetrahydrofuran solvent, stirring and dissolving, then continuously adding a boron trifluoride diethyl etherate catalyst, reacting for 2-4 hours at 20-25 ℃, continuously adding sodium hydroxide into the mixture for ring closure reaction, heating to 60-70 ℃ for reacting for 3-4 hours, centrifuging and separating after the reaction is finished, and washing with n-hexane for 2-3 times to obtain fluorine-containing modified epoxy resin;
the mass ratio of the p-hydroxybenzaldehyde to the o-aminotrifluorotoluene in the step (1) is 1:1.1-1.3;
The mass ratio of the intermediate 1, 4-amino-3-fluorobenzene mercaptan to benzoin dimethyl ether photoinitiator in the step (2) is 1.2-1.3:1:0.02-0.03;
The mass ratio of the intermediate 2 to the polyethylene glycol to the epichlorohydrin to the boron trifluoride diethyl etherate catalyst to the sodium hydroxide in the step (3) is 0.8-1.2:1:2.8-3.5:0.04-0.06:0.05-0.07.
2. The preparation method of the high-temperature-resistant fluoroelastomer processing aid for the slurry process polyethylene process according to claim 1, wherein the preparation method of the high-temperature-resistant fluoroelastomer processing aid for the slurry process polyethylene process comprises the steps of adding graphene oxide modified epoxy resin, fluorine-containing modified epoxy resin and tetrafluoroethylene-vinylidene fluoride copolymer into a double-screw extruder, extruding at 170-180 ℃ and at an extrusion speed of 50-60min, crushing the extrudate, extracting with acetone for 6-9h, filtering and drying to obtain the high-temperature-resistant fluoroelastomer processing aid for the slurry process polyethylene process.
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| CN1649941A (en) * | 2001-02-16 | 2005-08-03 | 杜邦唐弹性体公司 | Process aid for melt processable polymers |
| CN117327364A (en) * | 2023-11-07 | 2024-01-02 | 稷昶新材料科技(上海)有限公司 | Fluorine-containing plastic processing aid and preparation process thereof |
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| CN109135014A (en) * | 2018-08-19 | 2019-01-04 | 福建师范大学泉港石化研究院 | A kind of fluoropolymer aid master batches with elimination melt fracture effect |
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