CN117510916B - Preparation method of high-temperature-resistant modified polyethylene isolating film - Google Patents
Preparation method of high-temperature-resistant modified polyethylene isolating film Download PDFInfo
- Publication number
- CN117510916B CN117510916B CN202311462455.0A CN202311462455A CN117510916B CN 117510916 B CN117510916 B CN 117510916B CN 202311462455 A CN202311462455 A CN 202311462455A CN 117510916 B CN117510916 B CN 117510916B
- Authority
- CN
- China
- Prior art keywords
- mixture
- modified polyethylene
- modified
- temperature
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 75
- -1 polyethylene Polymers 0.000 title claims abstract description 75
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 67
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 37
- 239000004952 Polyamide Substances 0.000 claims abstract description 33
- 229920002647 polyamide Polymers 0.000 claims abstract description 33
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 28
- 239000011574 phosphorus Substances 0.000 claims abstract description 28
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 24
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims abstract description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 12
- RFRNGRYAJCOIAN-UHFFFAOYSA-N 5-ethenylbenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C=C)=CC(C(O)=O)=C1 RFRNGRYAJCOIAN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000748 compression moulding Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 76
- 239000000203 mixture Substances 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- 239000002904 solvent Substances 0.000 claims description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 238000005406 washing Methods 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- YCTNWTBGSOCMRO-UHFFFAOYSA-N 3,5-dinitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC(C=O)=CC([N+]([O-])=O)=C1 YCTNWTBGSOCMRO-UHFFFAOYSA-N 0.000 claims description 11
- PDCMTKJRBAZZHL-UHFFFAOYSA-N 5-aminobenzene-1,3-diol Chemical compound NC1=CC(O)=CC(O)=C1 PDCMTKJRBAZZHL-UHFFFAOYSA-N 0.000 claims description 11
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims 3
- 238000004821 distillation Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 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 11
- 239000003063 flame retardant Substances 0.000 abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- 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
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of polyethylene, and discloses a preparation method of a high-temperature-resistant modified polyethylene isolating film, wherein m-phenylenediamine, isophthaloyl dichloride and phosphorus-containing m-phenylenediamine are subjected to polycondensation reaction to obtain modified polyamide. The carboxyl in the 5-vinyl isophthalic acid and the thiol group of KH590 modified nano-silica are subjected to catalytic esterification under the condition of p-toluenesulfonic acid to obtain vinyl nano-silica, and the vinyl nano-silica, maleic anhydride and polyethylene react under the initiation of dicumyl peroxide to obtain the modified polyethylene. And finally, uniformly mixing the modified polyethylene and the modified polyamide, extruding, granulating and compression molding to obtain the modified polyethylene isolating film. The modified polyethylene isolating film prepared by the invention has excellent mechanical property, flame retardant property and high temperature resistance.
Description
Technical Field
The invention relates to the technical field of polyethylene isolating films, in particular to a preparation method of a high-temperature-resistant modified polyethylene isolating film.
Background
Polyethylene is thermoplastic resin prepared by polymerization reaction of ethylene monomer, has excellent low temperature resistance, chemical stability, electrical insulation and other performances, and is widely applied to the fields of packaging materials, films, wires, cables and the like, but has poor mechanical properties.
Polyamide is commonly called nylon, is a generic name of thermoplastic resin with a molecular main chain containing repeated amide groups, has excellent mechanical property, heat resistance, abrasion resistance and other properties, is widely applied to the fields of engineering plastics, knitwear, medical supplies and the like, is subjected to blending modification with other substances, and can improve the comprehensive performance of the composite material so as to expand the application range of the composite material.
The phosphorus-containing flame retardant is a high-efficiency, smokeless and low-pollution flame retardant. Silica is an inorganic compound, has excellent fire resistance, high temperature resistance, corrosion resistance and other properties, and is widely applied to the fields of glass, electronic industry, optical instruments, refractory materials and the like.
The invention discloses a preparation method of a heat-resistant polyethylene-nylon composite film, which is characterized in that hyperbranched imide polyamide is prepared by blending and modifying the hyperbranched imide polyamide and nylon, and the prepared polyethylene-nylon composite film has high thermal decomposition temperature and strong thermal stability, but does not improve the mechanical property and flame retardant property.
Disclosure of Invention
(One) solving the technical problems
Aiming at the defects of the prior art, the invention provides a preparation method of a high-temperature-resistant modified polyethylene isolating film.
(II) technical scheme
A preparation method of a high-temperature-resistant modified polyethylene isolating film comprises the following steps:
(1) Adding m-phenylenediamine, isophthaloyl dichloride and phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of between-10 and-5 ℃ under the nitrogen condition, heating to 20-35 ℃, reacting for 20-60min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(2) Adding vinyl nano silicon dioxide, maleic anhydride and dicumyl peroxide into an acetone solvent, adding polyethylene into the acetone solvent, uniformly stirring, heating to 180-240 ℃, reacting for 5-20min, and drying after the reaction is finished to obtain the modified polyethylene.
(3) Mixing the dried modified polyethylene and modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃,200 ℃, 210 ℃, 230 ℃ and the screw speed is 40-70r/min, granulating, and compression molding to obtain the modified polyethylene isolating film.
Preferably, in the step (1), the mass ratio of the m-phenylenediamine to the m-phthaloyl chloride to the phosphorus-containing m-phenylenediamine is 100:180-240:5-20.
Preferably, in the step (2), the mass ratio of the vinyl nano silicon dioxide to the maleic anhydride to the dicumyl peroxide to the polyethylene is 1-3:2-4:0.5-1.5:100.
Preferably, in the step (3), the mass ratio of the modified polyethylene to the modified polyamide is 100:80-120.
Preferably, in the step (1), the preparation method of phosphorus-containing m-phenylenediamine comprises the following steps:
s1, adding 3, 5-dinitrobenzaldehyde and 5-aminoresorcinol into an ethanol solvent, adding a glacial acetic acid catalyst into the ethanol solvent, heating to 60-80 ℃, carrying out reflux reaction for 5-12h, cooling to room temperature after the reaction is finished, filtering, washing with deionized water, and recrystallizing with ethanol to obtain an intermediate 1.
S2, adding the intermediate 1 and triethylamine into a toluene solvent under the condition of nitrogen, adding diphenyl phosphorus chloride into the toluene solvent at the temperature of between minus 5 and 0 ℃, stirring and dispersing, heating to the temperature of between 60 and 80 ℃, reacting for 2 to 5 hours, cooling to room temperature after the reaction is finished, filtering, distilling filtrate under reduced pressure, and recrystallizing acetonitrile to obtain the intermediate 2.
S3, adding the intermediate 2 and Pd/C into an ethanol solvent under the condition of nitrogen, heating to 40-50 ℃, adding 70-80% hydrazine hydrate into the mixture, carrying out reflux reaction for 2-5h, filtering, washing with deionized water, and recrystallizing with ethanol to obtain phosphorus-containing m-phenylenediamine.
Preferably, in the step S1, the mass ratio of the 3, 5-dinitrobenzaldehyde to the 5-aminoresorcinol is 100:60-80.
Preferably, in the step S2, the molar ratio of the intermediate 1 to the triethylamine to the diphenyl phosphorus chloride is 100:5-15:140-180.
Preferably, in the step S3, the mass ratio of the intermediate 2 to Pd/C is 100:3-5.
Preferably, in the step (2), the preparation method of the vinyl nano silica comprises the following steps: adding 5-vinyl isophthalic acid, KH590 modified nano-silica and p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 100-120 ℃, reacting for 10-20h, decompressing and distilling after the reaction is finished, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
Preferably, in the step, the molar ratio of the 5-vinyl isophthalic acid, the KH590 modified nano-silica and the p-toluenesulfonic acid is 100:200-250:18-24.
(III) beneficial technical effects
3, 5-Dinitrobenzaldehyde and 5-aminoresorcinol are subjected to Schiff base preparation reaction to obtain an intermediate 1, the intermediate 1 is reacted with diphenyl phosphorus chloride under the catalysis of triethylamine to obtain an intermediate 2, and nitro is reduced to amino under the reduction catalysis of Pd/C to obtain phosphorus-containing m-phenylenediamine. And (3) performing polycondensation reaction on the m-phenylenediamine, the m-phthaloyl chloride and the phosphorus-containing m-phenylenediamine to obtain the modified polyamide. The carboxyl in the 5-vinyl isophthalic acid and the thiol group of KH590 modified nano-silica are subjected to catalytic esterification under the condition of p-toluenesulfonic acid to obtain vinyl nano-silica, and the vinyl nano-silica, maleic anhydride and polyethylene react under the initiation of dicumyl peroxide to obtain the modified polyethylene. And finally, uniformly mixing the modified polyethylene and the modified polyamide, extruding, granulating and compression molding to obtain the modified polyethylene isolating film.
The modified polyethylene isolating film prepared by the invention contains modified polyethylene and modified polyamide, and because the compatibility of the polyethylene and the polyamide is poor, the polyethylene prepared by the invention contains maleic anhydride groups, and side chain groups of the modified polyethylene and the modified polyamide are mutually crosslinked and wound to form more crosslinking sites, and when the modified polyethylene isolating film is impacted, impact energy is mutually transmitted along the crosslinking sites, so that the mechanical property of the material is improved.
The nano silicon dioxide used in the invention is easy to agglomerate, has better dispersibility after organic modification, reduces agglomeration, has better compatibility with organic matters after organic modification, and can be better dispersed in organic media. In addition, the modified polyethylene isolating film contains more silica bonds, the bond energy of the silica bonds is larger than that of carbon-carbon bonds, when the modified polyethylene isolating film is impacted, the silica bonds can absorb more impact energy so as to enhance the mechanical property of the modified polyethylene isolating film, and as the nano silica can be uniformly dispersed in organisms after being organically modified, the crosslinking degree of the nano silica and organism molecules is increased, the binding force at an interface is increased, and when the material is impacted, the nano silica can play a role of stress concentration points and triggering generation of silver pattern shearing bands, so that the mechanical property of the modified polyethylene isolating film is further improved.
The modified polyethylene isolating film prepared by the invention contains silicon element, phosphorus element and nitrogen element. When heated, the phosphorus element contained in the material is heated to generate acidic substances such as phosphoric acid, metaphosphoric acid and the like, so that the material can be promoted to be dehydrated to form carbon, a compact carbon layer is formed, and along with the rise of the temperature, the phosphoric acid and metaphosphoric acid further form polymetaphosphoric acid, and the polymetaphosphoric acid covers the surface of the material; the silicon element contained in the carbon layer has larger silicon-oxygen bond energy, can absorb more heat, and can form a continuous and oxidation-resistant silicate protective layer due to the rise of temperature, so that the silicon-oxygen bond in the carbon layer covers the surface of the material to block the material from transporting and transferring the external substances; the nitrogen element contained in the flame-retardant material can generate flame-retardant gas and dilute the concentration of flammable gas in the air, and the flame-retardant property of the flame-retardant material is improved by the cooperation of the nitrogen element, the flame-retardant material and the air.
The modified polyethylene isolating film prepared by the invention contains modified polyamide, the polyamide macromolecule chain is broken and decomposed into small units when heated at high temperature, and then the small units are subjected to polycondensation to form aromatic compounds with larger structures, so that the high temperature resistance of the material is improved, and in addition, the strong interface effect between the inorganic nano silicon dioxide and the material matrix can limit the thermal movement of the molecular chain segments of the material matrix, and the high temperature resistance of the material can also be improved. The modified polyethylene isolating film prepared by the invention has excellent mechanical property, flame retardant property and high temperature resistance.
Drawings
FIG. 1 shows a preparation route of phosphorus-containing metaphenylene diamine.
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.
Preparation of KH590 modified nano-silica: adding 10g of nano silicon dioxide into 30% ethanol solution, stirring and dispersing, adjusting the pH to 4 by using hydrochloric acid, adding 0.15g of KH590 into the solution, heating to 80 ℃, reacting for 10 hours, cooling to room temperature, filtering, washing and drying to obtain the KH590 modified nano silicon dioxide.
Example 1
(1) 5G of 3, 5-dinitrobenzaldehyde and 3.8g of 5-aminoresorcinol are added into ethanol solvent, 6mL of glacial acetic acid catalyst is added into the mixture, the temperature is raised to 75 ℃, the reflux reaction is carried out for 12 hours, the mixture is cooled to room temperature after the reaction is finished, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain an intermediate 1.
(2) Under the condition of nitrogen, 20g of intermediate 1 and 3g of triethylamine are added into toluene solvent, 35g of diphenyl phosphorus chloride is added into the toluene solvent at the temperature of minus 5 ℃, the mixture is stirred and dispersed, the temperature is raised to 80 ℃ for 2 hours of reaction, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filtrate is distilled under reduced pressure, and acetonitrile is recrystallized, thus obtaining intermediate 2.
(3) 15G of intermediate 2 and 0.6g of Pd/C are added into ethanol solvent under the condition of nitrogen, the temperature is raised to 50 ℃, 80% hydrazine hydrate is added into the solvent, the mixture is subjected to reflux reaction for 4 hours, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain phosphorus-containing m-phenylenediamine.
(4) Adding 30g of m-phenylenediamine, 60g of m-phthaloyl chloride and 1.5g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 5 ℃ under the nitrogen condition, heating to 35 ℃, reacting for 45min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(5) Adding 2g of 5-vinyl isophthalic acid, 4.2g of KH590 modified nano-silica and 0.45g of p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 110 ℃, reacting for 18h, decompressing and distilling, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
(6) Adding 0.5g of vinyl nano silicon dioxide, 1.8g of maleic anhydride and 0.6g of dicumyl peroxide into an acetone solvent, adding 50g of polyethylene into the mixture, uniformly stirring the mixture, heating the mixture to 200 ℃, reacting the mixture for 15min, and drying the mixture after the reaction is finished to obtain the modified polyethylene.
(7) Mixing 200g of dried modified polyethylene and 160g of modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 60r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
Example 2
(1) 5G of 3, 5-dinitrobenzaldehyde and 3.2g of 5-aminoresorcinol are added into an ethanol solvent, 4.5mL of glacial acetic acid catalyst is added into the ethanol solvent, the temperature is raised to 60 ℃, the reflux reaction is carried out for 10 hours, the reaction is finished, the reaction is cooled to room temperature, the filtration and the washing with deionized water are carried out, and the ethanol is recrystallized, thus obtaining an intermediate 1.
(2) Under the condition of nitrogen, 20g of intermediate 1 and 2.5g of triethylamine are added into toluene solvent, 30g of diphenyl phosphorus chloride is added into the toluene solvent at the temperature of minus 5 ℃, stirred and dispersed, the temperature is raised to 75 ℃ for reaction for 5 hours, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filtrate is distilled under reduced pressure, and acetonitrile is recrystallized, so that intermediate 2 is obtained.
(3) 15G of intermediate 2 and 0.7g of Pd/C are added into ethanol solvent under the condition of nitrogen, the temperature is raised to 50 ℃, 70% hydrazine hydrate is added into the mixture, the mixture is subjected to reflux reaction for 2 hours, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain phosphorus-containing m-phenylenediamine.
(4) Adding 30g of m-phenylenediamine, 54g of m-phthaloyl chloride and 3g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 5 ℃ under the nitrogen condition, heating to the temperature of 30 ℃, reacting for 60min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(5) Adding 2g of 5-vinyl isophthalic acid, 4.5g of KH590 modified nano-silica and 0.48g of p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 110 ℃, reacting for 15h, decompressing and distilling, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
(6) Adding 0.75g of vinyl nano silicon dioxide, 1.8g of maleic anhydride and 0.3g of dicumyl peroxide into an acetone solvent, adding 50g of polyethylene into the mixture, stirring the mixture uniformly, heating the mixture to 240 ℃, reacting the mixture for 10min, and drying the mixture after the reaction is finished to obtain the modified polyethylene.
(7) Mixing 200g of dried modified polyethylene and 180g of modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 60r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
Example 3
(1) 5G of 3, 5-dinitrobenzaldehyde and 3.6g of 5-aminoresorcinol are added into ethanol solvent, 5mL of glacial acetic acid catalyst is added into the mixture, the temperature is raised to 70 ℃, the reflux reaction is carried out for 10 hours, the mixture is cooled to room temperature after the reaction is finished, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain an intermediate 1.
(2) Under the condition of nitrogen, 20g of intermediate 1 and 3g of triethylamine are added into a toluene solvent, 28g of diphenyl phosphorus chloride is added into the toluene solvent at the temperature of 0 ℃, the mixture is stirred and dispersed, the temperature is raised to 80 ℃, the reaction is carried out for 3 hours, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filtrate is distilled under reduced pressure, and acetonitrile is recrystallized, thus obtaining intermediate 2.
(3) 15G of intermediate 2 and 0.6g of Pd/C are added into ethanol solvent under the condition of nitrogen, the temperature is raised to 45 ℃, 75% hydrazine hydrate is added into the solvent, the mixture is subjected to reflux reaction for 5 hours, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain phosphorus-containing m-phenylenediamine.
(4) Adding 30g of m-phenylenediamine, 72g of m-phthaloyl chloride and 4.5g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 5 ℃ under the nitrogen condition, heating to 35 ℃, reacting for 20min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(5) Adding 2g of 5-vinyl isophthalic acid, 4.6g of KH590 modified nano-silica and 0.4g of p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 120 ℃, reacting for 10 hours, decompressing and distilling, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
(6) Adding 1g of vinyl nano silicon dioxide, 1.6g of maleic anhydride and 0.5g of dicumyl peroxide into an acetone solvent, adding 50g of polyethylene into the mixture, uniformly stirring the mixture, heating the mixture to 200 ℃, reacting the mixture for 20min, and drying the mixture after the reaction is finished to obtain the modified polyethylene.
(7) Mixing 200g of dried modified polyethylene and 200g of modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 70r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
Example 4
(1) 5G of 3, 5-dinitrobenzaldehyde and 4g of 5-aminoresorcinol are added into ethanol solvent, 6mL of glacial acetic acid catalyst is added into the ethanol solvent, the temperature is raised to 80 ℃, the reflux reaction is carried out for 6 hours, the reaction is cooled to room temperature after the reaction is finished, the mixture is filtered, washed by deionized water, and ethanol is recrystallized to obtain an intermediate 1.
(2) Under the condition of nitrogen, 20g of intermediate 1 and 1.9g of triethylamine are added into toluene solvent, 35g of diphenyl phosphorus chloride is added into the toluene solvent at the temperature of minus 5 ℃, the mixture is stirred and dispersed, the temperature is raised to 80 ℃ for 2 hours of reaction, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filtrate is distilled under reduced pressure, and acetonitrile is recrystallized, so that intermediate 2 is obtained.
(3) 15G of intermediate 2 and 0.75g of Pd/C are added into ethanol solvent under the condition of nitrogen, the temperature is raised to 40 ℃, 78% hydrazine hydrate is added into the solvent, the mixture is subjected to reflux reaction for 5 hours, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain phosphorus-containing m-phenylenediamine.
(4) Adding 30g of m-phenylenediamine, 60g of m-phthaloyl chloride and 5g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 5 ℃ under the nitrogen condition, heating to 35 ℃, reacting for 50min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(5) Adding 2g of 5-vinyl isophthalic acid, 4g of KH590 modified nano-silica and 0.48g of p-toluenesulfonic acid into a toluene solvent, stirring and dispersing, heating to 100 ℃, reacting for 20 hours, decompressing and distilling, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
(6) Adding 1.25g of vinyl nano silicon dioxide, 2g of maleic anhydride and 0.25g of dicumyl peroxide into an acetone solvent, adding 50g of polyethylene into the mixture, uniformly stirring the mixture, heating the mixture to 240 ℃, reacting the mixture for 20min, and drying the mixture after the reaction is finished to obtain the modified polyethylene.
(7) Mixing 200g of dried modified polyethylene and 220g of modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃,200 ℃, 210 ℃, 230 ℃ and the screw speed is 50r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
Example 5
(1) 5G of 3, 5-dinitrobenzaldehyde and 3g of 5-aminoresorcinol are added into ethanol solvent, 6mL of glacial acetic acid catalyst is added into the ethanol solvent, the temperature is raised to 80 ℃, the reflux reaction is carried out for 10 hours, the reaction is cooled to room temperature after the reaction is finished, the mixture is filtered, washed by deionized water, and ethanol is recrystallized to obtain an intermediate 1.
(2) Under the condition of nitrogen, 20g of intermediate 1 and 2.5g of triethylamine are added into a toluene solvent, 36g of diphenyl phosphorus chloride is added into the toluene solvent at 0 ℃, the mixture is stirred and dispersed, the temperature is raised to 70 ℃ for 5 hours of reaction, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filtrate is distilled under reduced pressure, and acetonitrile is recrystallized, so that intermediate 2 is obtained.
(3) 15G of intermediate 2 and 0.6g of Pd/C are added into ethanol solvent under the condition of nitrogen, the temperature is raised to 50 ℃, 80% hydrazine hydrate is added into the solvent, the mixture is subjected to reflux reaction for 5 hours, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain phosphorus-containing m-phenylenediamine.
(4) Adding 30g of m-phenylenediamine, 60g of m-phthaloyl chloride and 6g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 10 ℃ under the nitrogen condition, heating to 30 ℃, reacting for 60min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(5) Adding 2g of 5-vinyl isophthalic acid, 5g of KH590 modified nano-silica and 0.4g of p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 120 ℃, reacting for 12 hours, decompressing and distilling, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
(6) Adding 1.5g of vinyl nano silicon dioxide, 1.8g of maleic anhydride and 0.6g of dicumyl peroxide into an acetone solvent, adding 50g of polyethylene into the mixture, stirring the mixture uniformly, heating the mixture to 220 ℃, reacting the mixture for 20min, and drying the mixture after the reaction is finished to obtain the modified polyethylene.
(7) Mixing 200g of dried modified polyethylene and 240g of modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃,200 ℃, 210 ℃, 230 ℃ and the screw speed is 50r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
Comparative example 1
(1) Adding 2g of 5-vinyl isophthalic acid, 4.2g of KH590 modified nano-silica and 0.45g of p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 110 ℃, reacting for 18h, decompressing and distilling, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
(2) Adding 0.5g of vinyl nano silicon dioxide, 1.8g of maleic anhydride and 0.6g of dicumyl peroxide into an acetone solvent, adding 50g of polyethylene into the mixture, uniformly stirring the mixture, heating the mixture to 200 ℃, reacting the mixture for 15min, and drying the mixture after the reaction is finished to obtain the modified polyethylene.
(3) Adding 30g of m-phenylenediamine, 60g of m-phthaloyl chloride and 1.5g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 5 ℃ under the nitrogen condition, heating to 35 ℃, reacting for 45min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(4) Mixing 200g of dried modified polyethylene and 160g of modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃,200 ℃, 210 ℃, 230 ℃ and the screw speed is 60r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
Comparative example 2
(1) 5G of 3, 5-dinitrobenzaldehyde and 3.8g of 5-aminoresorcinol are added into ethanol solvent, 6mL of glacial acetic acid catalyst is added into the mixture, the temperature is raised to 75 ℃, the reflux reaction is carried out for 12 hours, the mixture is cooled to room temperature after the reaction is finished, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain an intermediate 1.
(2) Under the condition of nitrogen, 20g of intermediate 1 and 3g of triethylamine are added into toluene solvent, 35g of diphenyl phosphorus chloride is added into the toluene solvent at the temperature of minus 5 ℃, the mixture is stirred and dispersed, the temperature is raised to 80 ℃ for 2 hours of reaction, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filtrate is distilled under reduced pressure, and acetonitrile is recrystallized, thus obtaining intermediate 2.
(3) 15G of intermediate 2 and 0.6g of Pd/C are added into ethanol solvent under the condition of nitrogen, the temperature is raised to 50 ℃, 80% hydrazine hydrate is added into the solvent, the mixture is subjected to reflux reaction for 4 hours, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain phosphorus-containing m-phenylenediamine.
(4) Adding 30g of m-phenylenediamine, 60g of m-phthaloyl chloride and 1.5g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 5 ℃ under the nitrogen condition, heating to 35 ℃, reacting for 45min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(5) Mixing dry polyethylene 200g and modified polyamide 160g uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 60r/min, granulating, and compression molding to obtain the modified polyethylene isolating film.
And testing the mechanical properties of the material by using an electronic universal tester.
Tensile Strength (MPa) | Tensile modulus (GPa) | |
Example 1 | 16.92 | 0.34 |
Example 2 | 18.49 | 0.39 |
Example 3 | 20.64 | 0.46 |
Example 4 | 24.71 | 0.51 |
Example 5 | 22.30 | 0.49 |
Comparative example 1 | 15.64 | 0.26 |
Comparative example 2 | 14.93 | 0.21 |
As can be seen from the table, the mechanical properties of examples 1 to 5 are better than those of comparative examples 1 and 2, because the polyamide has fewer side chain groups and less entanglement with polyethylene in comparative example 1, and thus has poorer mechanical properties than examples 1 to 5, and the nanosilica is not contained in comparative example 2, and thus has poorer mechanical properties than examples 1 to 5.
The high temperature resistance of the material was tested using a heat distortion Vicat softening point tester, wherein the rate of temperature rise was 100 ℃/h.
Heat distortion temperature (DEG C) | |
Example 1 | 60 |
Example 2 | 64 |
Example 3 | 76 |
Example 4 | 85 |
Example 5 | 82 |
Comparative example 1 | 58 |
Comparative example 2 | 45 |
The heat resistance of examples 1-5 and comparative example 1 is better than that of comparative example 2 because the absence of nanosilica in comparative example 2, the strong interface between nanosilica and the material matrix can limit thermal movement of the molecular segments of the material matrix.
The limiting oxygen index of the material was measured using an oxygen index meter.
The horizontal vertical burn rating of the material was tested using a horizontal vertical burner.
As can be seen from the table, the flame retardant properties of examples 1 to 5 are better than those of comparative examples 1 and 2.
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 (5)
1. The preparation method of the high-temperature-resistant modified polyethylene isolating film is characterized by comprising the following steps of:
(1) Adding m-phenylenediamine, isophthaloyl chloride and phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of between-10 ℃ and-5 ℃ under the condition of nitrogen, wherein the mass ratio of the m-phenylenediamine to the isophthaloyl chloride to the phosphorus-containing m-phenylenediamine is 100:180-240:5-20, heating to 20-35 ℃, reacting for 20-60min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain modified polyamide, wherein the preparation method of the phosphorus-containing m-phenylenediamine comprises the following steps:
s1, adding 3, 5-dinitrobenzaldehyde and 5-aminoresorcinol into an ethanol solvent, adding a glacial acetic acid catalyst into the ethanol solvent, heating to 60-80 ℃, carrying out reflux reaction for 5-12h, cooling to room temperature after the reaction is finished, filtering, washing with deionized water, and recrystallizing with ethanol to obtain an intermediate 1;
S2, adding the intermediate 1 and triethylamine into a toluene solvent under the condition of nitrogen, adding diphenyl phosphorus chloride into the toluene solvent at the temperature of between minus 5 and 0 ℃, stirring and dispersing, heating to the temperature of between 60 and 80 ℃, reacting for 2 to 5 hours, cooling to room temperature after the reaction is finished, filtering, distilling filtrate under reduced pressure, and recrystallizing acetonitrile to obtain an intermediate 2;
S3, adding the intermediate 2 and Pd/C into an ethanol solvent under the condition of nitrogen, heating to 40-50 ℃, adding 70-80% hydrazine hydrate into the solvent, carrying out reflux reaction for 2-5h, filtering, washing with deionized water, and recrystallizing with ethanol to obtain phosphorus-containing m-phenylenediamine;
(2) Adding vinyl nano silicon dioxide, maleic anhydride and dicumyl peroxide into an acetone solvent, wherein the mass ratio of the vinyl nano silicon dioxide to the maleic anhydride to the dicumyl peroxide to the polyethylene is 1-3:2-4:0.5-1.5:100, adding the polyethylene into the mixture, uniformly stirring the mixture, heating the mixture to 180-240 ℃, reacting the mixture for 5-20min, and drying the mixture after the reaction is finished to obtain modified polyethylene, wherein the preparation method of the vinyl nano silicon dioxide comprises the following steps: adding 5-vinyl isophthalic acid, KH590 modified nano-silica and p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 100-120 ℃, reacting for 10-20h, after the reaction is finished, performing reduced pressure distillation, washing with deionized water, and recrystallizing methanol to obtain vinyl nano-silica;
(3) Uniformly mixing the dried modified polyethylene and the modified polyamide, wherein the mass ratio of the modified polyethylene to the modified polyamide is 100:80-120, adding the mixture into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 40-70r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
2. The method for preparing a high temperature resistant modified polyethylene insulation film according to claim 1, wherein in the step S1, the mass ratio of 3, 5-dinitrobenzaldehyde to 5-aminoresorcinol is 100:60-80.
3. The method for preparing a high temperature resistant modified polyethylene isolating film according to claim 1, wherein in the step S2, the molar ratio of the intermediate 1 to triethylamine to diphenyl phosphorus chloride is 100:5-15:140-180.
4. The method for preparing a high temperature resistant modified polyethylene isolating film according to claim 1, wherein in the step S3, the mass ratio of the intermediate 2 to Pd/C is 100:3-5.
5. The method for producing a high temperature resistant modified polyethylene separator according to claim 1, wherein in the step (2), the molar ratio of 5-vinylisophthalic acid, KH590 modified nanosilica, p-toluenesulfonic acid is 100:200-250:18-24.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311462455.0A CN117510916B (en) | 2023-11-06 | 2023-11-06 | Preparation method of high-temperature-resistant modified polyethylene isolating film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311462455.0A CN117510916B (en) | 2023-11-06 | 2023-11-06 | Preparation method of high-temperature-resistant modified polyethylene isolating film |
Publications (2)
Publication Number | Publication Date |
---|---|
CN117510916A CN117510916A (en) | 2024-02-06 |
CN117510916B true CN117510916B (en) | 2024-05-10 |
Family
ID=89746860
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311462455.0A Active CN117510916B (en) | 2023-11-06 | 2023-11-06 | Preparation method of high-temperature-resistant modified polyethylene isolating film |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117510916B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05339407A (en) * | 1992-06-11 | 1993-12-21 | Tonen Chem Corp | Production of fuel tank |
EP0583595A1 (en) * | 1992-07-20 | 1994-02-23 | Bayer Ag | Impact resistant, optionally filled polyamide mixtures with polyamide-polyethylene laminated film wastes |
US6025423A (en) * | 1994-09-28 | 2000-02-15 | Elf Atochem S.A. | Flame-retardant thermoplastic compositions for electrical cable coatings |
CN108017852A (en) * | 2017-12-22 | 2018-05-11 | 安徽华塑股份有限公司 | A kind of high-strength polyvinyl chloride resin and preparation method thereof |
CN108314818A (en) * | 2018-01-19 | 2018-07-24 | 四川厚诚新材料有限公司 | A kind of delustring curtain coating PE films and preparation method thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6623866B2 (en) * | 2001-04-04 | 2003-09-23 | Exxonmobil Oil Corporation | Multilayer films including anti-block |
-
2023
- 2023-11-06 CN CN202311462455.0A patent/CN117510916B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05339407A (en) * | 1992-06-11 | 1993-12-21 | Tonen Chem Corp | Production of fuel tank |
EP0583595A1 (en) * | 1992-07-20 | 1994-02-23 | Bayer Ag | Impact resistant, optionally filled polyamide mixtures with polyamide-polyethylene laminated film wastes |
US6025423A (en) * | 1994-09-28 | 2000-02-15 | Elf Atochem S.A. | Flame-retardant thermoplastic compositions for electrical cable coatings |
CN108017852A (en) * | 2017-12-22 | 2018-05-11 | 安徽华塑股份有限公司 | A kind of high-strength polyvinyl chloride resin and preparation method thereof |
CN108314818A (en) * | 2018-01-19 | 2018-07-24 | 四川厚诚新材料有限公司 | A kind of delustring curtain coating PE films and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN117510916A (en) | 2024-02-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4179551A (en) | Low temperature curable compliant bismaleimide compositions | |
JP6022475B2 (en) | Polymer raw materials and polymers | |
US4269961A (en) | Low temperature curable compliant bismaleimide compositions | |
CN115260491B (en) | Alkali-resistant hydrolysis-resistant polyimide engineering plastic and preparation method thereof | |
CN102219902A (en) | Polymide molding powder and preparation method thereof | |
CN117510916B (en) | Preparation method of high-temperature-resistant modified polyethylene isolating film | |
KR20210044488A (en) | Method for manufacturing PI-Silica composite material using Silane coupling agent | |
CN111117240A (en) | Preparation method of novel composite polyimide flame-retardant sheet material | |
JP2947094B2 (en) | Method for producing high molecular weight polyamide-imide resin | |
CN115386085B (en) | Polyester imide copolymer and preparation method and application thereof | |
CN117164854A (en) | Cross-linked polyimide and preparation method thereof | |
CN113429782B (en) | Transparent polyamide resin and preparation method thereof | |
CN112760735A (en) | Flame-retardant polyamide fiber | |
KR100689182B1 (en) | Manufacturing method of polyamideimide | |
KR100483712B1 (en) | Polyamideimide polymer for enamel copper wire covering and enamel copper wire manufacturing method | |
CN116082728B (en) | Flame-retardant wire and cable insulator sheath material | |
CN117844214A (en) | Flame-retardant polylactic acid resin composition and preparation method thereof | |
CN115716914A (en) | Imidization method of polyamide acid and polyimide | |
CN116239865A (en) | Polyimide-coated inorganic particle modified epoxy resin and preparation method thereof | |
KR100277161B1 (en) | Novel aromatic polyimide resin powder with improved processability and preparation method thereof | |
CN116239790A (en) | Carboxyl end-capped hyperbranched polyamide based on furandicarboxylic acid, preparation method and application thereof | |
CN117164622A (en) | Preparation method and application of flame-retardant plasticizer | |
JPS5821649B2 (en) | Fuhouwa Polyester Keiji Yushino Seizouhouhou | |
CN115895542A (en) | Flame-retardant high-temperature-resistant adhesive preparation and preparation method thereof | |
CN117903591A (en) | Preparation method of flame-retardant nylon for new energy automobile and product thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |