CN116217927A - Modified triazine charring agent and preparation method thereof, and environment-friendly intumescent flame retardant polypropylene material and preparation method thereof - Google Patents
Modified triazine charring agent and preparation method thereof, and environment-friendly intumescent flame retardant polypropylene material and preparation method thereof Download PDFInfo
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- CN116217927A CN116217927A CN202310000475.XA CN202310000475A CN116217927A CN 116217927 A CN116217927 A CN 116217927A CN 202310000475 A CN202310000475 A CN 202310000475A CN 116217927 A CN116217927 A CN 116217927A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 83
- 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 title claims abstract description 81
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 75
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 75
- -1 polypropylene Polymers 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 41
- 150000003918 triazines Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 34
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 28
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 22
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 22
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 22
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000011787 zinc oxide Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- OYIFNHCXNCRBQI-UHFFFAOYSA-N 2-aminoadipic acid Chemical compound OC(=O)C(N)CCCC(O)=O OYIFNHCXNCRBQI-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002245 particle Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 238000004383 yellowing Methods 0.000 abstract description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002341 toxic gas Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 20
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 14
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 13
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
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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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- 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
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a modified triazine charring agent and a preparation method thereof, and an environment-friendly intumescent flame retardant polypropylene material and a preparation method thereof. The structural formula of the modified triazine charring agent is shown as follows:
wherein R is 1 is-CH 2 CH 2 ‑，R 2 Is that
Description
Technical Field
The invention relates to the field of flame-retardant materials, in particular to a char former and an environment-friendly intumescent flame-retardant polypropylene material.
Background
Polypropylene (PP) is used as a general plastic, and is widely applied to industries such as furniture, packaging, automobiles, buildings and the like due to excellent mechanical properties, processability and lower cost. However, the main chain and the side chain of the polypropylene are both carbon chain structures, the polypropylene is extremely easy to burn, potential fire hazards exist in the use process, and along with the higher fireproof requirements of polypropylene products, the improvement of the flame retardant property of the polypropylene material becomes an urgent need and development trend.
The flame retardant is added to improve the flame retardant property of the polypropylene material, is a simple and efficient method, and is currently the most mainstream flame retardant, but the flame retardant contains a large amount of halogen and has the defects of large smoke quantity, toxic gas generation and the like. The expansion flame retardant (IFR) is a halogen-free flame retardant system, has low smoke and low toxicity in the combustion process, and is an important development direction of future flame retardants. The intumescent flame retardant mainly comprises an acid source, a carbon source and a gas source, and realizes heat insulation and oxygen insulation through solid phase expansion into carbon, thereby finally achieving the aim of flame retardance. The char former is the basis for the expansion and carbonization layer, and the earliest use of polyhydroxy compounds typified by pentaerythritol. CN105255016B uses pentaerythritol stearate as a char forming agent, and is matched with ammonium polyphosphate and melamine to form an intumescent flame retardant and prepare a halogen-free flame retardant master batch special for polypropylene, but the char forming agent is easy to migrate out in the use process due to high water solubility, so that the flame retardant effect is poor. CN113549216a is prepared from cyanuric chloride, monoamine and diamine, and is prepared by synthesizing macromolecular triazine charring agent; CN105418675B discloses that hypophosphorous acid, diethanolamine and formaldehyde undergo mannich reaction under the catalysis of aqueous phase and hydrochloric acid, and then melamine is added to react with triazine char forming agent. CN102585347B uses a silicon-containing triazine macromolecular char former combined with acid sources such as ammonium polyphosphate to form an intumescent flame retardant and uses the intumescent flame retardant to prepare a flame retardant polypropylene mixture, which exhibits good flame retardant and water resistance. At present, triazine charring agent has high chlorine content generally, hydrogen chloride is released in the use process, amino groups at the tail ends of molecular chains are oxidized to cause yellowing of products, the compatibility of the flame retardant and a PP matrix is poor, and the mechanical property of a polypropylene material is reduced by adding the flame retardant, so that the application field and the application effect of the material are greatly limited.
Disclosure of Invention
The invention aims to overcome the defects of the existing intumescent flame retardant polypropylene material and provides a modified triazine charring agent and a preparation method thereof, and an environment-friendly intumescent flame retardant polypropylene material and a preparation method thereof. Compared with the traditional triazine charring agent product, the modified macromolecule triazine charring agent has the advantages of low chlorine content, good thermal stability, high whiteness and difficult yellowing. The polypropylene material has good compatibility, excellent flame retardant property and excellent mechanical property, and can be widely applied to industries such as automobiles, buildings and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an environment-friendly intumescent flame retardant polypropylene material comprises the following components in parts by weight:
the polypropylene resin is one or more of homo-polypropylene and co-polypropylene, and the melt index is 3-110g/10min, such as WH-HP456J, WH-EP548R, WH-EP648V, WH-HP648T of Wanhua chemistry.
As a preferable scheme, the mass ratio of the ammonium polyphosphate to the modified triazine charring agent is 1:1-5:1.
The preparation method of the modified triazine charring agent comprises the following steps:
(1) Condensation of cyanuric chloride with ethanolamine and ethylenediamine: dripping ethanolamine solution into the mixture of cyanuric chloride, acetone and deionized water at 3-10 ℃ for 0.5-1h; heating to 50-55 ℃, dropwise adding a first part of ethylenediamine solution, reacting for 0.5-1h, heating to 95-100 ℃, dropwise adding a second part of ethylenediamine solution, and reacting for 0.5-1h;
(2) Modification end-capping: and (3) dropwise adding an L-2-aminoadipic acid solution into the reaction solution obtained in the step (1), reacting for 0.5-1h, cooling, filtering and drying.
In the step (1), the mole ratio of cyanuric chloride, ethanolamine and ethylenediamine is 1:0.8-1.2:0.5-1.
In the step (1), the ethanolamine solution is ethanolamine, sodium hydroxide and deionized water according to the following weight ratio of 1:0.8-1.2:2-5 mole ratio.
In the step (1), the ethylenediamine solution is ethylenediamine, sodium hydroxide and deionized water according to the following weight ratio of 1:2-2.5:10-15 mol ratio.
In the step (1), the mass ratio of the first part of ethylenediamine solution to the second part of ethylenediamine solution is 1-2:1.
in the step (2), the molar ratio of the L-2-aminoadipic acid to the cyanuric chloride in the step (1) is 0.2-0.5:1.
in the step (2), the L-2-aminoadipic acid solution, sodium hydroxide and deionized water are mixed according to the following weight ratio of 1:1-2:10-15 mol ratio.
The structural formula of the modified triazine charring agent is shown as follows:
wherein R is 1 is-CH 2 CH 2 -，R 2 Is that
The antioxidant is one or more of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010), tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076) and 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (antioxidant 3114).
The average grain diameter of the nano zinc oxide is 50+/-10 nm.
The preparation method of the environment-friendly intumescent flame retardant polypropylene material comprises the following steps:
(1) Uniformly mixing polypropylene resin, ammonium polyphosphate, a modified triazine charring agent, an antioxidant and nano zinc oxide;
(2) And (3) putting the mixed raw materials into a double-screw extruder, and performing melt extrusion granulation to obtain the environment-friendly intumescent flame retardant polypropylene material.
Preferably, the step (1) is carried out in a stirrer at a rotating speed of 50-100r/min and stirring for 20-30min.
Preferably, the temperatures of each section of the double-screw extruder are respectively as follows: 180+ -5 ℃, 190+ -5 ℃, 200+ -5 ℃, 210+ -5 ℃, 220+ -5 ℃ and the screw rotation speed of 50-100r/min
The modified triazine charring agent is a charring agent which is difficult to dissolve in water and can simultaneously play roles of a carbon source and a gas source, and the ammonium polyphosphate realizes high-efficiency flame retardance on the polymer through a mechanism of forming an expanded carbon layer and catalyzing and increasing the carbon. The intumescent flame retardant compounded by the modified triazine charring agent and the ammonium polyphosphate has excellent flame retardant effect, and the water resistance and mechanical property of the flame retardant material are also obviously improved.
The invention has the beneficial effects that: (1) The flame-retardant polypropylene material is prepared by using the intumescent flame retardant compounded by the modified triazine charring agent which has good water resistance, low chlorine content, high whiteness and yellowing resistance and ammonium polyphosphate, and has good compatibility, difficult precipitation, good thermal stability, less hydrogen chloride toxic gas release and more excellent flame retardant property in the use process. (2) The nano zinc oxide is used as a synergistic flame retardant, so that the flame retardant property of the material is improved, the addition amount of the intumescent flame retardant is reduced, the mechanical property of the material is improved as a reinforcing material, and the influence of the flame retardant on the mechanical property of the material is reduced. Can be widely applied to industries such as automobiles, buildings and the like
Drawings
FIG. 1 is an infrared spectrum of the modified triazine char-forming agent prepared in example 1.
Detailed Description
The following detailed description of the present invention is provided in connection with specific embodiments, which are intended to be illustrative of the invention and not limiting of the scope of the invention.
The environment-friendly intumescent flame retardant polypropylene material prepared by the invention performs performance test according to the national standard test method:
1. flame retardant performance test: limiting Oxygen Index (LOI) tests were performed according to GB/T2406-2009 standards with sample sizes of 100mm by 6.5mm by 1.6mm; vertical Combustion (UL-94) was tested according to the GB/T2408-1996 standard with sample sizes of 100mm by 13mm by 1.6mm.
2. Mechanical property test: tensile strength and elongation at break were determined according to GB/T1840-1992; notched Izod impact strength was measured according to GB/T1843-1996.
Example 1
The synthesis method of the modified triazine charring agent comprises the following steps:
(1) 110.7g (0.6 mol) of cyanuric chloride, 100mL of acetone and 100mL of deionized water were added sequentially to a four-necked flask, and the temperature was maintained at 5 ℃. An additional 30.5g (0.5 mol) of ethanolamine, 18g (0.45 mol) of sodium hydroxide and 50mL of deionized water were taken to prepare an ethanolamine solution, and the ethanolamine solution was slowly added dropwise into the flask and allowed to react for 1 hour.
(2) 30g (0.4 mol) of ethylenediamine, 36g (0.9 mol) of sodium hydroxide and 100mL of deionized water are prepared into an ethylenediamine solution, and half of the ethylenediamine solution is slowly dripped at 50 ℃ to react for 1 hour. And then heating to 95 ℃, slowly dripping the other half of ethylenediamine solution, and fully polycondensing for 1h to obtain an intermediate.
(3) A mixed solution of 32.2g (0.2 mol) of L-2-aminoadipic acid, 12g (0.3 mol) of sodium hydroxide and 50mL of deionized water was prepared, and the mixed solution was slowly added dropwise to the reaction system, followed by complete reaction for 1 hour. Cooling, suction filtering and drying to obtain the required modified triazine charring agent, wherein the structural formula is as follows:
-CH 2 CH 2 -
the environment-friendly flame-retardant polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene resin WH-EP648V, 15 parts of ammonium polyphosphate Aladin-A189185, 10 parts of modified triazine charring agent, 0.04 part of antioxidant 1010, 0.03 part of antioxidant 168 and 2 parts of nano zinc oxide.
The raw materials with the weight portions are put into a stirrer to be uniformly mixed, the rotating speed is 80r/min, and the stirring is carried out for 30min. Putting the mixed raw materials into a double-screw extruder, and performing melt extrusion granulation to obtain the environment-friendly intumescent flame retardant polypropylene material, wherein the temperatures of each section of the double-screw extruder are respectively as follows: 180 ℃, 190 ℃, 200 ℃, 210 ℃ (220 ℃ (temperature fluctuation < 5 ℃), screw rotation speed 80r/min.
Example 2
The environment-friendly flame-retardant polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene resin WH-EP648V, 15 parts of ammonium polyphosphate Aladin-A189185, 5 parts of modified triazine charring agent of example 1, 0.04 part of antioxidant 1010, 0.03 part of antioxidant 168 and 2 parts of nano zinc oxide. An environment-friendly intumescent flame retardant polypropylene material was prepared according to the method of example 1.
Example 3
The environment-friendly flame-retardant polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene resin WH-EP648V, 12 parts of ammonium polyphosphate Aladin-A189185, 8 parts of modified triazine charring agent of example 1, 0.04 part of antioxidant 1010, 0.03 part of antioxidant 168 and 2 parts of nano zinc oxide. An environment-friendly intumescent flame retardant polypropylene material was prepared according to the method of example 1.
Example 4
The environment-friendly flame-retardant polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene resin WH-EP648V, 18 parts of ammonium polyphosphate Aladin-A189185, 12 parts of modified triazine charring agent of example 1, 0.04 part of antioxidant 1010, 0.03 part of antioxidant 168 and 2 parts of nano zinc oxide. An environment-friendly intumescent flame retardant polypropylene material was prepared according to the method of example 1.
Example 5
The environment-friendly flame-retardant polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene resin WH-EP648V, 15 parts of ammonium polyphosphate Aladin-A189185, 10 parts of modified triazine charring agent of example 1, 0.04 part of antioxidant 1010, 0.03 part of antioxidant 168 and 1 part of nano zinc oxide. An environment-friendly intumescent flame retardant polypropylene material was prepared according to the method of example 1.
Example 6
The environment-friendly flame-retardant polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene resin WH-EP648V, 15 parts of ammonium polyphosphate Aladin-A189185, 10 parts of modified triazine charring agent of example 1, 0.04 part of antioxidant 1010, 0.03 part of antioxidant 168 and 3 parts of nano zinc oxide. An environment-friendly intumescent flame retardant polypropylene material was prepared according to the method of example 1.
Example 7
The environment-friendly flame-retardant polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene resin WH-EP648V, 15 parts of ammonium polyphosphate Aladin-A189185, 10 parts of modified triazine charring agent of example 1, 0.04 part of antioxidant 1010, 0.03 part of antioxidant 168 and 4 parts of nano zinc oxide. An environment-friendly intumescent flame retardant polypropylene material was prepared according to the method of example 1.
Comparative example 7-1
The synthesis method of the triazine charring agent comprises the following steps:
(1) 110.7g (0.6 mol) of cyanuric chloride, 100mL of acetone and 100mL of deionized water were added sequentially to a four-necked flask, and the temperature was maintained at 5 ℃. An additional 30.5g (0.5 mol) of ethanolamine, 18g (0.45 mol) of sodium hydroxide and 50mL of deionized water were taken to prepare an ethanolamine solution, and the ethanolamine solution was slowly added dropwise into the flask and allowed to react for 1 hour.
(2) 30g (0.4 mol) of ethylenediamine, 36g (0.9 mol) of sodium hydroxide and 100mL of deionized water are prepared into an ethylenediamine solution, and half of the ethylenediamine solution is slowly dripped at 50 ℃ to react for 1 hour. And then heating to 95 ℃, slowly dripping the other half of ethylenediamine solution, fully polycondensing for 1h, cooling, filtering and drying to obtain the required triazine charring agent.
The flame-retardant polypropylene material comprises the following raw materials in parts by mass: 100 parts of polypropylene resin WH-EP648V, 15 parts of ammonium polyphosphate Aladin-A189185, 10 parts of triazine charring agent, 0.04 part of antioxidant 1010, 0.03 part of antioxidant 168 and 4 parts of nano zinc oxide. An environment-friendly intumescent flame retardant polypropylene material was prepared according to the method of example 1.
Comparative example 1
The environment-friendly flame-retardant polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene resin WH-EP648V, 15 parts of ammonium polyphosphate Aladin-A189185, 10 parts of modified triazine charring agent, 0.04 part of antioxidant 1010 and 0.03 part of antioxidant 168. An environment-friendly intumescent flame retardant polypropylene material was prepared according to the method of example 1.
Comparative example 2
The environment-friendly flame-retardant polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene resin WH-EP648V, 15 parts of ammonium polyphosphate Aladin-A189185, 10 parts of pentaerythritol, 0.04 part of antioxidant 1010, 0.03 part of antioxidant 168 and 2 parts of nano zinc oxide. An environment-friendly intumescent flame retardant polypropylene material was prepared according to the method of example 1.
Comparative example 3
The environment-friendly flame-retardant polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene resin WH-EP648V, 10 parts of modified triazine charring agent, 0.04 part of antioxidant 1010, 0.03 part of antioxidant 168 and 2 parts of nano zinc oxide. An environment-friendly intumescent flame retardant polypropylene material was prepared according to the method of example 1.
Comparative example 4
The environment-friendly flame-retardant polypropylene material comprises the following raw materials in parts by weight: 100 parts of polypropylene resin WH-EP648V, 0.04 part of antioxidant 1010, 0.03 part of antioxidant 168 and 2 parts of zinc oxide. An environment-friendly intumescent flame retardant polypropylene material was prepared according to the method of example 1.
The results of the performance tests of the examples and the comparative examples are shown in Table 1.
Table 1 test results for examples and comparative examples
As can be seen from Table 1, the environment-friendly intumescent flame retardant polypropylene material prepared by the invention has excellent flame retardant property, the flame retardant property of the flame retardant polypropylene material prepared by several examples reaches FV-0 level, the limiting oxygen index is above 29.6%, and the maximum oxygen index can reach 32.7%. In addition, the prepared flame-retardant polypropylene material has excellent mechanical property, the tensile strength is more than 29.3MPa, the maximum tensile strength can reach 32.2MPa, and the notch impact strength is 2.7 kJ.m -2 The maximum value of the catalyst can be 3.8 kJ.m -2 . As can be seen from comparison of examples 1, 5, 6, 7 and 1, the addition of nano zinc oxide not only improves the flame retardant property of the material, but also significantly improves the mechanical properties of the material. As can be seen from comparison of example 1, comparative example 7-1 and comparative examples 2, 3 and 4, compared with the traditional intumescent flame retardant system consisting of ammonium polyphosphate and pentaerythritol, ammonium polyphosphate single component and common triazine char-forming agent single component, the intumescent flame retardant compounded by using ammonium polyphosphate and modified triazine char-forming agent can enable the material to obtain more excellent flame retardant performance, the limiting oxygen index is improved from 29.5% to 32.5%, and the UL94 test grade is improved from FV-1 to FV-0.
Claims (10)
1. A modified triazine charring agent has a structural formula shown as follows:
wherein R is 1 is-CH 2 CH 2 -，R 2 Is that
2. The process for preparing a modified triazine char-forming agent according to claim 1, comprising the steps of:
(1) Condensation of cyanuric chloride with ethanolamine and ethylenediamine: dripping ethanolamine solution into the mixture of cyanuric chloride, acetone and deionized water at 3-10 ℃ for 0.5-1h; heating to 50-55 ℃, dropwise adding a first part of ethylenediamine solution, reacting for 0.5-1h, heating to 95-100 ℃, dropwise adding a second part of ethylenediamine solution, and reacting for 0.5-1h;
(2) Modification end-capping: and (3) dropwise adding an L-2-aminoadipic acid solution into the reaction solution obtained in the step (1), reacting for 0.5-1h, cooling, filtering and drying.
3. The method according to claim 2, characterized in that: in the step (1), the mole ratio of cyanuric chloride, ethanolamine and ethylenediamine is 1:0.8-1.2:0.5-1.
4. The method according to claim 2, characterized in that: in the step (2), the molar ratio of the L-2-aminoadipic acid to the cyanuric chloride in the step (1) is 0.2-0.5:1.
5. an environment-friendly intumescent flame retardant polypropylene material comprises the following components in parts by weight:
6. the environmentally friendly intumescent flame retardant polypropylene material of claim 5, wherein: the polypropylene resin is one or more of homo-polypropylene and co-polypropylene, and the melt index is 3-110g/10min, preferably WH-HP456J, WH-EP548R, WH-EP648V, WH-HP648T of Wanhua chemistry.
7. The environmentally friendly intumescent flame retardant polypropylene material of claim 5 or 6, wherein: the mass ratio of the ammonium polyphosphate to the modified triazine charring agent is 1:1-5:1.
8. The environmentally friendly intumescent flame retardant polypropylene material of any one of claims 5-7, wherein: the antioxidant is one or more of 1010, 168, 1076 and 3114.
9. The environmentally friendly intumescent flame retardant polypropylene material of any one of claims 5-8, wherein: the average particle size of the nano zinc oxide is 50+/-10 nm.
10. A process for preparing the environmentally friendly expanded flame retardant polypropylene of any one of claims 5-9, comprising the steps of:
(1) Uniformly mixing polypropylene resin, ammonium polyphosphate, a modified triazine charring agent, an antioxidant and nano zinc oxide;
(2) And (3) putting the mixed raw materials into a double-screw extruder, and performing melt extrusion granulation to obtain the environment-friendly intumescent flame retardant polypropylene material.
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