CN116285002A - Nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant, and preparation method and application thereof - Google Patents
Nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant, and preparation method and application thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 85
- 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 82
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000010703 silicon Substances 0.000 title claims abstract description 42
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 42
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000006757 chemical reactions by type Methods 0.000 title claims abstract description 27
- 238000009396 hybridization Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- 239000002808 molecular sieve Substances 0.000 claims abstract description 27
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003365 glass fiber Substances 0.000 claims abstract description 25
- 229920006351 engineering plastic Polymers 0.000 claims abstract description 16
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000010992 reflux Methods 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
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- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
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- 238000002156 mixing Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
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- 229960004050 aminobenzoic acid Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CSEWAUGPAQPMDC-UHFFFAOYSA-N 2-(4-aminophenyl)acetic acid Chemical compound NC1=CC=C(CC(O)=O)C=C1 CSEWAUGPAQPMDC-UHFFFAOYSA-N 0.000 description 1
- HAAUVXXFRQXTTQ-UHFFFAOYSA-N 2-[4-(azaniumylmethyl)phenyl]acetate Chemical compound NCC1=CC=C(CC(O)=O)C=C1 HAAUVXXFRQXTTQ-UHFFFAOYSA-N 0.000 description 1
- OCSPARJUBMYNLY-UHFFFAOYSA-N 3,9-dichloro-2,4,8,10-tetraoxa-3$l^{5},9$l^{5}-diphosphaspiro[5.5]undecane 3,9-dioxide Chemical compound C1OP(Cl)(=O)OCC21COP(Cl)(=O)OC2 OCSPARJUBMYNLY-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QCTBMLYLENLHLA-UHFFFAOYSA-N aminomethylbenzoic acid Chemical compound NCC1=CC=C(C(O)=O)C=C1 QCTBMLYLENLHLA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001821 azanediyl group Chemical group [H]N(*)* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000007865 diluting Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
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- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides an nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant, and a preparation method and application thereof. The flame retardant is synthesized by esterification reaction of SBA-15 mesoporous molecular sieve and PPTR or homologues with 2 or 4 methylene. The flame retardant prepared by the invention has reactive groups, improves the compatibility with polyamide, reduces the candle wick effect of glass fiber, and can realize flame retardant modification of glass fiber reinforced polyamide engineering plastics under lower addition.
Description
Technical Field
The invention belongs to the field of flame retardants, and particularly relates to a nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant, and a preparation method and application thereof.
Background
The polyamide engineering plastic has the advantages of high strength, good temperature resistance, excellent electrical insulation performance, oil resistance, wear resistance and the like, is widely applied to the fields of electronics and electrics, mechanics, automobiles, chemical engineering and the like, and is one of engineering plastics with the largest yield in the world. The glass fiber reinforced polyamide can greatly improve the strength and the heat distortion temperature, is an effective way for manufacturing the high-strength heat-resistant polyamide, but generates a candlewick effect when in combustion, reduces the flame retardant grade of the polyamide, and limits the application of the polyamide in the fields of electricity, traffic and the like, so the flame retardance of the glass fiber reinforced polyamide is always a focus of attention in the polymer flame retardance field.
At present, the flame retardant used for flame retardant modification of glass fiber reinforced polyamide is mainly phosphorus and nitrogen, and has the defects of large addition (generally 15-35%wt) and deterioration of the mechanical properties of the polymer body. Intumescent Flame Retardants (IFR) are new flame retardants developed on the basis of conventional flame retardants, generally consisting of an acid source (p=o), a carbon source (C-C, ar) and a gas source (NH 2 N=c) three structural units. Compared with the traditional flame retardant, the IFR has the advantages of high flame retardant efficiency, environmental friendliness, no halogen and the like, but also has the problems of poor bulk density, low dispersity, poor carbonization effect, no hydrolysis resistance and the like of a polymer body, and has non-negligible influence on mechanical properties such as tensile strength, impact strength and the like of the body material. In order to further improve the flame retardant efficiency of the intumescent flame retardant, researchers combine the IFR with the silicon flame retardant, connect flame retardant groups with siloxane together through organic-inorganic hybridization means, exert advantages such as stable structure of Si-O-Si bond, high temperature resistance, good hydrothermal stability, and the like, and prepare the novel flame retardant with the characteristics of high efficiency, low toxicity, drip resistance, easy carbon formation, smoke suppression, and the like. Among them, mesoporous silicon SBA-15 has attracted more and more attention as a synergist of flame retardants. Mesoporous silicon SBA-15 has a uniform pore structureThe porous polymer has the advantages of large specific surface area, high porosity, good thermal stability and hydrothermal stability, can keep the stability of the framework in the high-temperature combustion process, has pore diameters capable of containing molecular chains of the polymer, has abundant active groups such as hydroxyl on the surface, and the like, is suitable for modification, and can also hybridize or adsorb functional compounds in the framework and pores. Based on the characteristics, mesoporous silicon SBA-15 is used as a synergist and is researched in the flame retardant field of polymers such as polyethylene, polypropylene, polycarbonate, epoxy resin, polystyrene, polylactic acid and the like, and the effects of inhibiting combustion and fuming, improving water resistance and mechanical properties and the like can be achieved by adding a small amount of the mesoporous silicon SBA-15.
However, the mesoporous silicon SBA-15 is used as a synergist alone, the use effect is limited, the addition amount of the intumescent flame retardant IFR is still large (10-25%wt), the compatibility with a polymer body is not improved, the IFR, the mesoporous silicon SBA-15 and the polymer body material are respectively phase-formed, the flame retardant and the synergist cannot be uniformly dispersed in the polymer body, the flame retardant efficiency is greatly reduced, and the IFR is easy to separate out or dissolve out. Thus, glass fiber reinforced polyamide materials currently are not flame retardant with high requirements (e.g., UL 94V-0 grade) using intumescent flame retardants.
Disclosure of Invention
The invention aims at solving the problems of flame retardance of the existing glass fiber reinforced polyamide engineering plastics, and provides a nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant which does not contain halogen, has a porous structure and a larger pore diameter, can accommodate polyamide molecular chains, has carboxyl functional groups capable of being chemically bonded with the polyamide molecular chains, has high hydrothermal stability and solvent resistance, has abundant hydroxyl groups on the surface of mesoporous silicon and can be bonded with the hydroxyl groups on the surface of glass fibers through hydrogen bonds, so that the flame retardant can be highly dispersed in the glass fiber reinforced polyamide engineering plastics, has excellent flame retardance and anti-dripping performance, can obviously reduce the addition of the flame retardant, and improves the mechanical property of the flame retardant polyamide engineering plastics.
A nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant has a structural formula shown in formula 1:
wherein SBA-15-phi is a mesoporous molecular sieve, the mass fraction of the mesoporous molecular sieve in the flame retardant is 10% -20%, and the pore diameter of the micropore in the mesoporous molecular sieve silicon dioxide is 10-30 nm; r is R 1 -PPTR-R 2 Is 4,4' - ((3, 9-dioxa-2, 4,8,10-tetraoxa-3, 9-diphosphatapiro [ 5.5)]A homolog of undecan-3, 9-diyl) bis (aza nediyl)) dibenzoic acid (PPTR when a=0 and b=0; when a and/or b=1, are homologs of PPTR), the mass fraction in the flame retardant is 80% to 90%.
The second purpose of the invention is to provide a preparation method of the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant, which comprises the following specific steps:
(1) Dissolving a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer (P123) in deionized water, adding ethyl silicate (TEOS) and hydrochloric acid, continuously and vigorously stirring for 24-48 hours, filling into a polytetrafluoroethylene bottle for crystallization for 24-48 hours, filtering, washing with water, drying, calcining at 520-580 ℃ for 5-8 hours to remove TEOS, and filtering, washing with water and drying to obtain a white powdery SBA-15 mesoporous molecular sieve; wherein, the mol ratio of TEOS, P123, hydrochloric acid and deionized water is 1: (0.1-0.5): (5-15): (130-150);
preferably, the temperature when ethyl silicate (TEOS) and hydrochloric acid are added is 35-40 ℃;
(2) Pentaerythritol and phosphorus oxychloride are mixed according to a mole ratio of 1:3, heating to 60-90 ℃ under the protection of nitrogen, stirring, heating to 100-110 ℃ for reflux reaction, distilling under reduced pressure to remove unreacted phosphorus oxychloride, and drying to constant weight to obtain a white powdery intermediate product 3, 9-dichloro-2, 4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane 3, 9-dioxide (DCDP for short), wherein the structural formula is shown in formula 2:
preferably, the stirring time is 80 to 120 minutes;
preferably, the reflux reaction time is 10 to 12 hours;
(3) The compound shown in the formula 3-1 and DCDP are mixed according to the mol ratio of 2:1 to 2.6:1, mixing, adding a solvent and a catalyst, heating and refluxing under the protection of nitrogen, filtering, washing and drying to obtain a compound with a structural formula shown in a formula 3;
in the formula 3-1 and the formula 3, R 1 、R 2 Is methylene, a=0 or 1, b=0 or 1;
preferably, the solvent is one of ethyl acetate or glacial acetic acid, and the addition amount of the solvent is 3-5 times of the mass of the para-aminobenzoic acid or the homolog thereof;
preferably, the catalyst is triethylamine;
(4) Mixing a compound shown in a formula 3 with an SBA-15 mesoporous molecular sieve, wherein the mass ratio of the compound to the SBA-15 mesoporous molecular sieve is 90: 10-80: 20, adding a solvent and a catalyst 4-dimethylaminopyridine; adding 2-3 times of ethylene glycol diethyl ether as solvent, heating for esterification reaction for 6-24 hours, filtering, washing and drying to obtain nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant shown in formula 1;
preferably, the solvent is ethylene glycol diethyl ether, and the addition amount of the solvent is 2-3 times of the total mass of the compound shown in the formula 3 and the SBA-15 mesoporous molecular sieve.
The invention further aims to provide a flame-retardant glass fiber reinforced polyamide engineering plastic, which comprises 10-15% of the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant; the rest is glass fiber reinforced polyamide engineering plastic, wherein the mass fraction of the glass fiber is 20-30% of the total mass, and the rest is polyamide resin. The flame-retardant glass fiber reinforced polyamide engineering plastic is prepared by fully mixing nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant and glass fiber reinforced polyamide engineering plastic slices, and carrying out melt blending extrusion and granulating by a double-screw extruder.
Compared with the prior art, the invention has the following advantages:
1. the nitrogen-phosphorus hybrid reaction type mesoporous silicon flame retardant provided by the invention contains nitrogen, phosphorus and silicon ternary flame retardant groups, wherein nitrogen element can be converted into nitrogen to play a role in diluting oxygen in a gas phase, phosphorus element can be converted into free radicals, oxides or phosphates to play a role in preventing flame propagation and isolating flame in a gas phase and a solid phase respectively, silicon element can be converted into silicon dioxide to play a role in isolating flame in a solid phase, and compared with the nitrogen-phosphorus binary flame retardant groups adopted in the prior art, the flame retardant provided by the invention has a better flame retardant effect;
2. in the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant provided by the invention, the pore size of the SBA-15 mesoporous molecular sieve is larger (the pore size is more than or equal to 10nm and less than or equal to 30 nm), a polyamide molecular chain can enter the pore of the molecular sieve and be combined with a molecular chain outside the pore to form a network structure, the acting force of a polyamide body and a molecular sieve interface is enhanced, the compatibility of the flame retardant and the polyamide body is improved, and compared with the prior art, the addition amount of the flame retardant in the polyamide is obviously reduced (the mass fraction of the optimal embodiment is 10 percent), and the mechanical property of a flame retardant polyamide product is obviously improved;
3. the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant provided by the invention has carboxyl reaction active groups, and can be subjected to polycondensation reaction with polyamide molecular chains with amino active groups to form firm chemical bonds, so that the compatibility of the flame retardant and polyamide is essentially improved, and the precipitation phenomenon of the flame retardant frequently occurring in the melt processing process or the solvent soaking process is avoided;
4. the SBA-15 mesoporous molecular sieve surface in the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant provided by the invention contains abundant hydroxyl groups, can be combined with the hydroxyl groups on the glass fiber surface in a hydrogen bond mode and is covered on the glass fiber surface to reduce the 'candle core effect', and compared with the prior art, the flame retardant prepared by the invention can effectively improve the flame retardant property of glass fiber reinforced polyamide;
5. the SBA-15 mesoporous molecular sieve pore wall in the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant provided by the invention has excellent heat insulation, hydrolysis resistance and solvent resistance, and nitrogen and phosphorus flame retardant elements are firmly combined with the SBA-15 mesoporous molecular sieve and a polyamide main chain through chemical bonds;
6. the preparation method provided by the invention is simple, mature and easy for industrial production.
Drawings
FIG. 1 is a flow chart of the method of the present invention.
Detailed Description
Examples are given below to further illustrate the invention. It is to be noted that the following examples are not to be construed as limiting the scope of the invention, and that if a person skilled in the art makes some insubstantial modifications and adaptations of the invention based on the above description, they still fall within the scope of the invention.
The flame retardant properties of the flame retardant glass fiber reinforced polyamide engineering plastic samples used in the following examples were determined by the UL94 vertical burning method; the tensile strength is measured by using GB/T1447-2005 fiber reinforced plastic tensile property test method; the notch impact strength is measured by a method of GB/T1843-2008 "measurement of impact Strength of Plastic cantilever beam".
Example 1: preparation of mesoporous silicon flame retardant PPTR/SBA-15-30
(1) 324g (18 mol) of deionized water and 188g (1.8 mol) of concentrated hydrochloric acid were added to a 1L round-bottom flask and mixed thoroughly, respectively, 20g (0.06 mol) of P123 preheated at 40℃was added dropwise to the above hydrochloric acid solution, heated and stirred in a water bath at 40℃for 4 hours until complete dissolution, then 25.06g (0.12 mol) of TEOS was slowly added dropwise, and stirred vigorously at 40℃for 48 hours. After the reaction is finished, transferring the mixed solution into a hydrothermal reaction kettle lined with polytetrafluoroethylene, placing the hydrothermal reaction kettle in a baking oven at 100 ℃ for crystallization for 48 hours, finally carrying out suction filtration, washing to pH 4-5 and drying on the obtained product, calcining the obtained white powder in a high-temperature furnace at 580 ℃ for 8 hours (the heating rate is 1K/min) to obtain 24.3g of SBA-15 mesoporous molecular sieve, and detecting that the aperture of the SBA-15 mesoporous molecular sieve is 29.6nm through a nitrogen adsorption-desorption experiment, namely SBA-15-30;
(2) 13.615g (0.1 mol) of pentaerythritol and 45.999g (0.3 mol) of phosphorus oxychloride are added into a 100mL three-neck round bottom flask, a thermometer and a reflux condenser are connected, the mixture is heated to 60 ℃ under the protection of nitrogen, stirred for 80min, heated to 105 ℃ for reflux reaction for 10h, unreacted phosphorus oxychloride is removed by reduced pressure distillation, and dried to constant weight, thus obtaining a white powdery intermediate product 3, 9-dichloro-2, 4,8,10-tetraoxa-3,9-diphosphaspiro [5.5]]28.784g of undecane 3, 9-dioxide (DCDP for short), 1 H NMR(400MHz，DMSO-d6)δ4.23ppm， 31 p (122 MHz, chlorine-d) delta-3.09 ppm, structural formula as follows:
(3) 28.784g (0.097 mol) DCDP and 26.605g (0.194 mol) para-aminobenzoic acid are added into a 250mL four-neck round bottom flask, 79.815g ethyl acetate and 0.294g (0.003 mol) triethylamine are added, one port of the four-neck flask is connected with a reflux condenser, one port is connected with a tail gas absorbing device, one port is inserted into a nitrogen pipe, nitrogen is continuously blown into the flask and kept at micro positive pressure of the reactor, mechanical stirring is started, slow heating is carried out until reflux is carried out, the reaction is maintained until no hydrogen chloride gas is released, the obtained white suspension is filtered, washed by ethyl acetate and deionized water in sequence, and dried to obtain 47.279g white product (PPTR for short), 1 h NMR (400 MHz, DMSO-d 6) delta 4.37-4.43,7.12-7.87ppm, structural formula:
(4) 24g (0.048 mol) of PPTR, 2.677g of SBA-15-30 and 0.176g (0.0014 mol) of 4-dimethylaminopyridine are taken and added into a 150mL three-neck round bottom flask, 53.354g of ethylene glycol diethyl ether, a thermometer, a reflux condenser and a water separator are connected, stirring is started, the mixture is slowly heated to reflux, the reaction is carried out for 6 hours, the reaction product is filtered, a filter cake is washed by the ethylene glycol diethyl ether and deionized water, the mixture is dried at 120 ℃ to obtain 24.668g of white fine powdery product, namely, nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant PPTR/SBA-15-30, and a thermogravimetric analysis experiment proves that the mass fraction of the PPTR is 88.7%.
Example 2: preparation of mesoporous silicon flame retardant CH 2 -PPTR/SBA-15-20
(1) 378g (21 mol) of deionized water and 156.3g (1.5 mol) of concentrated hydrochloric acid were added to each 1L round-bottomed flask and mixed thoroughly, 10g (0.03 mol) of P123 preheated at 40℃was added dropwise to the above hydrochloric acid solution, heated in a water bath at 40℃and stirred for 4 hours until completely dissolved, and then 31.33g (0.15 mol) of TEOS was slowly added dropwise and stirred vigorously at 40℃for 36 hours. After the reaction is finished, transferring the mixed solution into a hydrothermal reaction kettle lined with polytetrafluoroethylene, placing the hydrothermal reaction kettle in a baking oven at 100 ℃ for crystallization for 36 hours, finally carrying out suction filtration, washing to pH 4-5 and drying on the obtained product, calcining the obtained white powder in a high-temperature furnace at 550 ℃ for 6 hours (the heating rate is 1K/min) to obtain 30.74g of SBA-15 mesoporous molecular sieve, and detecting that the aperture of the mesoporous molecular sieve is 19.4nm through a nitrogen adsorption-desorption experiment, namely SBA-15-20;
(2) 28.784g of DCDP was prepared as in example 1 (2);
(3) 28.784g (0.097 mol) of DCDP and 30.791g (0.204 mol) of 4- (aminomethyl) benzoic acid are added into a 250mL four-port round-bottom flask, 123g of glacial acetic acid and 0.825g (0.008 mol) of triethylamine are added, one port of the four-port flask is connected with a reflux condenser pipe, one port is connected with a tail gas absorbing device, one port is inserted with a nitrogen pipe, nitrogen is continuously blown in and kept at a slight positive pressure of the reactor, mechanical stirring is started, slow heating is carried out until reflux is carried out, the reaction is kept until no hydrogen chloride gas is released, the obtained white suspension is filtered, and is washed and dried by glacial acetic acid and deionized water in sequence, thus 48.561g of white product (CH for short 2 -PPTR)， 1 HNMR (400 MHz, DMSO-d 6) delta 4.41-4.43,7.09-7.81ppm, structural formula as follows:
(4) 25.265g (0.048 mol) of CH 2 PPTR, 4.459g SBA-15-20, 0.232g (0.0019 mol) 4-dimethylaminopyridine were addedAdding 89.172g of ethylene glycol diethyl ether into a 250mL three-neck round bottom flask, connecting a thermometer, a reflux condenser and a water separator, starting stirring, slowly heating to reflux, reacting for 7h, filtering the reaction product, washing a filter cake with the ethylene glycol diethyl ether and deionized water, and drying at 120 ℃ to obtain 29.478g of white fine powder product, namely the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant CH as claimed in claim 1 2 PPTR/SBA-15-20, in which PPTR-CH is confirmed by thermogravimetric analysis experiments 2 Is 83.7% by mass.
Example 3: preparation of mesoporous silicon flame retardant PPTR-CH 2 /SBA-15-15
(1) 486g (27 mol) of deionized water and 156.4g (1.5 mol) of concentrated hydrochloric acid were added to each 1L round-bottomed flask and mixed thoroughly, 10g (0.03 mol) of P123 preheated at 40℃was added dropwise to the above hydrochloric acid solution, heated in a water bath at 40℃and stirred for 4 hours until completely dissolved, and then 41.67g (0.2 mol) of TEOS was slowly added dropwise and stirred vigorously at 40℃for 36 hours. After the reaction is finished, transferring the mixed solution into a hydrothermal reaction kettle lined with polytetrafluoroethylene, placing the hydrothermal reaction kettle in a baking oven at 100 ℃ for crystallization for 36 hours, finally carrying out suction filtration, washing to pH 4-5 and drying on the obtained product, calcining the obtained white powder in a high-temperature furnace at 550 ℃ for 6 hours (the heating rate is 1K/min) to obtain 40.86g of SBA-15 mesoporous molecular sieve, and detecting that the aperture of the mesoporous molecular sieve is 15.4nm through a nitrogen adsorption-desorption experiment, namely SBA-15-15;
(2) 28.784g of DCDP was prepared as in example 1 (2);
(3) 28.784g (0.097 mol) DCDP and 30.791g (0.204 mol) para-aminophenylacetic acid are added into a 250mL four-neck round bottom flask, 123g glacial acetic acid and 0.825g (0.008 mol) triethylamine are added, one port of the four-neck flask is connected with a reflux condenser, one port is connected with a tail gas absorbing device, one port is inserted into a nitrogen pipe, nitrogen is continuously blown into the flask and kept at micro positive pressure of the reactor, mechanical stirring is started, slow heating is carried out until reflux is carried out, the reaction is maintained until no hydrogen chloride gas is released, the obtained white suspension is filtered, and is washed and dried by glacial acetic acid and deionized water in sequence, thus 47.852g of white product (PPTR-CH for short) is obtained 2 )， 1 H NMR (400 MHz, DMSO-d 6) delta 4.12,4.38-4.42,7.11-7.86ppm, structural formula as follows:
(4) 25.265g (0.048 mol) of PPTR-CH are taken 2 4.459g SBA-15 and 0.232g (0.0019 mol) 4-dimethylaminopyridine are added into a 250mL three-neck round bottom flask, 89.172g ethylene glycol diethyl ether is added, a thermometer, a reflux condenser and a water separator are connected, stirring is started, the mixture is slowly heated to reflux, reaction is carried out for 7 hours, the reaction product is filtered, a filter cake is washed by ethylene glycol diethyl ether and deionized water, and is dried at 120 ℃ to obtain 29.527g of white fine powder product, namely the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant PPTR-CH according to claim 1 2 SBA-15-15, in which PPTR-CH is confirmed by thermogravimetric analysis experiments 2 The mass fraction of (2) was 82.9%.
Example 4: preparation of mesoporous silicon flame retardant CH 2 -PPTR-CH 2 /SBA-15-10
(1) 702g (39 mol) of deionized water and 156.7g (1.5 mol) of concentrated hydrochloric acid were added to a 1L round-bottom flask and mixed thoroughly, 10g (0.03 mol) of P123 preheated at 35℃was added dropwise to the above hydrochloric acid solution, heated in a water bath at 35℃and stirred for 4 hours until completely dissolved, then 62.66g (0.3 mol) of TEOS was slowly added dropwise, and strongly stirred at 35℃for 24 hours. After the reaction is finished, transferring the mixed solution into a hydrothermal reaction kettle lined with polytetrafluoroethylene, placing the hydrothermal reaction kettle in a baking oven at 100 ℃ for crystallization for 24 hours, finally carrying out suction filtration, washing to pH 4-5 and drying on the obtained product, calcining the obtained white powder in a high-temperature furnace at 520 ℃ for 5 hours (the heating rate is 1K/min) to obtain 62.13g of SBA-15 mesoporous molecular sieve, and detecting that the aperture of the SBA-15 mesoporous molecular sieve is 9.7nm through a nitrogen adsorption-desorption experiment, namely SBA-15-10;
(2) 28.784g of DCDP was prepared as in example 1 (2);
(3) 28.784g (0.097 mol) of DCDP and 41.653g (0.252 mol) of 4-aminomethylphenylacetic acid are added into a 500mL four-port round bottom flask, 208.265g of glacial acetic acid and 1.315g (0.013 mol) of triethylamine are added, one port of the four-port flask is connected with a reflux condenser tube, the other port is connected with a tail gas absorbing device, one port is inserted into a nitrogen pipe, nitrogen is continuously blown in, the micro-positive pressure of the reactor is kept, mechanical stirring is started, slow heating is carried out until reflux is carried out, and the reaction is maintained until no reaction existsThe hydrogen chloride gas was evolved, the resulting white suspension was filtered, washed sequentially with glacial acetic acid, deionized water, and dried to give 52.739g of a white product (abbreviated as CH) 2 -PPTR-CH 2 ) 1HNMR (400 MHz, DMSO-d 6) delta 4.12,4.41-4.43,7.11-7.86ppm, structural formula as follows:
(4) 26.612g (0.048 mol) of CH 2 -PPTR-CH 2 6.653g SBA-15-10, 0.293g (0.0024 mol) 4-dimethylaminopyridine are added into a 250mL three-neck round bottom flask, 166.325g ethylene glycol diethyl ether is added, a thermometer, a reflux condenser and a water separator are connected, stirring is started, the mixture is slowly heated to reflux for reaction for 24 hours, the reaction product is filtered, a filter cake is washed by ethylene glycol diethyl ether and deionized water, and dried at 120 ℃ to obtain 33.136g white fine powder product, namely the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant CH of claim 1 2 -PPTR-CH 2 SBA-15-10, in which CH is confirmed by thermogravimetric analysis experiments 2 The mass fraction of PPTR was 78.5%.
Example 5: preparation of PPTR/SBA-15-30 flame retardant 30% glass fiber reinforced polyamide 66 (PA 66GF 30)
Taking 2100g of polyamide 66 resin slice of nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant PPTR/SBA-15-3030g prepared in example 1, and fully stirring to uniformly disperse the flame retardant in the polyamide 66 resin slice; melt blending and extruding the polyamide resin slice mixed with the flame retardant through a 35-type double-screw extruder, and adding 900g of long glass fiber through a side feeding port to be co-extruded with the resin slice; the temperature of each section of the double-screw extruder is 225 ℃ in the I region, 235 ℃ in the II region, 245 ℃ in the III region, 245 ℃ in the IV region, 235 ℃ in the V region, 215 ℃ in the VI region, and the screw rotating speed is 60r/min; the extruded strip is subjected to water cooling, granulating by a rotary granulator and drying to obtain flame-retardant glass fiber reinforced polyamide 66 resin slices, wherein the mass fraction of the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant PPTR/SBA-15-30 is 10%; the flame-retardant chips were prepared into standard vertical combustion (0.8 mm) bars, tensile bars and notched impact bars by an injection molding machine, the injection molding temperature was 240 ℃, the mold temperature was 110 ℃, and the combustion test and the mechanical property test were performed, respectively, and the results are shown in Table 1.
Examples 6 to 11: flame-retardant glass fiber reinforced polyamide engineering plastic samples with different addition amounts were prepared according to the same method as in example 5, and the test results are summarized in table 1.
Comparative examples 1 and 2: PPTR and SBA-15-30 prepared in example 1 (3) and example 1 (1) are taken respectively, a glass fiber reinforced polyamide 66 (PA 66GF 30) engineering plastic sample is prepared according to the same method in example 5, and compared with example 5, the purpose is to test the flame retardant effect and mechanical property of PPTR and SBA-15 under the condition of single use, so as to verify the flame retardant property of the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant provided by the invention.
TABLE 1 flame retardant Effect and mechanical Property results of engineering plastics of examples 5-11 and comparative examples 1-2
Claims (9)
1. The nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant is characterized in that the structural formula of the flame retardant is shown as formula 1:
wherein SBA-15 is a mesoporous molecular sieve, the mass fraction of the mesoporous silicon flame retardant is 10-20%, and the aperture of micropores in the mesoporous molecular sieve is 10-30 nm; r is R 1 、R 2 Is methylene, a=0 or 1, b=0 or 1.
2. The method for preparing the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant according to claim 1, which is characterized by comprising the following steps:
(1) Dissolving a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer P123 in deionized water, adding ethyl silicate TEOS and hydrochloric acid, stirring for 24-48 hours, filling into a polytetrafluoroethylene bottle for crystallization for 24-48 hours, filtering, washing with water, drying, calcining at 520-580 ℃ for 5-8 hours to remove the ethyl silicate TEOS, and filtering, washing with water and drying to obtain the SBA-15 mesoporous molecular sieve; wherein, the mol ratio of TEOS, P123, hydrochloric acid and deionized water is 1: (0.1-0.5): (5-15): (130-150);
(2) Pentaerythritol and phosphorus oxychloride are mixed according to a mole ratio of 1:3, mixing, heating to 60-90 ℃ under the protection of nitrogen, stirring, heating to 100-110 ℃ for reflux reaction, and drying to constant weight after reduced pressure distillation to obtain an intermediate product DCDP with a structural formula shown in formula 2;
(3) The compound shown in the formula 3-1 and DCDP are mixed according to the mol ratio of (2-2.6): 1, mixing, adding a solvent and a catalyst, heating and refluxing under the protection of nitrogen, filtering, washing and drying to obtain a compound with a structural formula shown in a formula 3;
in the formula 3-1 and the formula 3, R 1 、R 2 Is methylene, a=0 or 1, b=0 or 1;
(4) Mixing a compound shown in a formula 3 with an SBA-15 mesoporous molecular sieve, adding a solvent and a catalyst according to the mass ratio of (90:10) - (80:20), reacting for 6-24 hours under the heating condition, filtering, washing and drying to obtain the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant.
3. The method according to claim 2, wherein the stirring time in the step (2) is 80 to 120 minutes.
4. The process according to claim 2, wherein the reflux reaction time in step (2) is 10 to 12 hours.
5. The preparation method according to claim 2, wherein the solvent in the step (3) is one of ethyl acetate and glacial acetic acid, and the addition amount is 3-5 times of the mass of the p-aminobenzoic acid or the homolog thereof.
6. The method according to claim 2, wherein the catalyst in the step (3) is triethylamine.
7. The preparation method of claim 2, wherein the solvent in the step (4) is ethylene glycol diethyl ether, and the addition amount of the solvent is 2-3 times of the total mass of the compound shown in the formula 3 and the SBA-15 mesoporous molecular sieve.
8. The method of claim 2, wherein the catalyst of step (4) is 4-dimethylaminopyridine.
9. A flame-retardant glass fiber reinforced polyamide engineering plastic, which is characterized by comprising the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant and glass fiber reinforced polyamide engineering plastic as claimed in claim 1; wherein the mass fraction of the nitrogen-phosphorus hybridization reaction type mesoporous silicon flame retardant is 10% -15%.
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