CN113956294A - Novel special polyformaldehyde flame retardant and preparation method thereof - Google Patents
Novel special polyformaldehyde flame retardant and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 85
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 79
- 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 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims abstract description 19
- UZVYOXJIYBLENY-UHFFFAOYSA-N benzene-1,3-diol;boric acid Chemical compound OB(O)O.OC1=CC=CC(O)=C1 UZVYOXJIYBLENY-UHFFFAOYSA-N 0.000 claims abstract description 18
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 216
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 98
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 75
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 239000013067 intermediate product Substances 0.000 claims description 51
- 239000008367 deionised water Substances 0.000 claims description 46
- 229910021641 deionized water Inorganic materials 0.000 claims description 46
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 34
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 16
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 14
- -1 polyoxymethylene Polymers 0.000 claims description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 238000010898 silica gel chromatography Methods 0.000 claims description 8
- 238000010025 steaming Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 4
- 229940124543 ultraviolet light absorber Drugs 0.000 abstract description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 2
- 238000006757 chemical reactions by type Methods 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000005034 decoration Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000003367 polycyclic group Chemical group 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000007259 addition reaction Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- 239000003963 antioxidant agent Substances 0.000 description 22
- 230000003078 antioxidant effect Effects 0.000 description 22
- 230000008034 disappearance Effects 0.000 description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- 239000004114 Ammonium polyphosphate Substances 0.000 description 10
- 229920000877 Melamine resin Polymers 0.000 description 10
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 10
- 229920001276 ammonium polyphosphate Polymers 0.000 description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a novel special polyformaldehyde flame retardant and a preparation method thereof, wherein cyanuric chloride, 2, 4-dihydroxy benzene boric acid, allyl bromide and DOPO are used as raw materials, and the novel special polyformaldehyde flame retardant is obtained through the steps of coupling, substitution and addition reaction; contains three-molecule reaction type flame retardant DOPO, high N content, hydroxyl structure, polycyclic structure capable of forming stable carbonization layer, etc.; the ultraviolet light absorber contains a triazine structure, and triazine is an ultraviolet light absorber with high efficiency, low color, high processing temperature, good compatibility and excellent broad spectrum, so that the base material can be endowed with excellent light aging resistance, and the service life of the material is prolonged; and more benzene rings and six-membered rings exist, so that the heat resistance and the mechanical strength of polyformaldehyde can be remarkable, the synergistic effect on improving the light aging resistance and the flame retardance is achieved, the high-efficiency flame retardance is realized, the high-efficiency ultraviolet absorption performance and the heat resistance are realized, and the material is particularly suitable for the fields of outdoor building decoration and the like.
Description
Technical Field
The invention relates to the technical field of flame retardants, and particularly relates to a novel special polyformaldehyde flame retardant and a preparation method thereof.
Background
Polyoxymethylene (POM) is an engineering plastic with excellent properties. The molecular chain has good flexibility, high structural regularity of the molecular chain and high crystallinity (70-85%). The high density and high crystallinity are the main reasons for the excellent performance of POM, such as large modulus, high hardness, good dimensional stability, creep resistance, outstanding fatigue resistance, low water absorption, good self-lubricity and wide application temperature range (-40 ℃ to +120 ℃). POM has been widely used in the fields of automobile industry, machine manufacturing, precision instruments, chemical industry, electrical communication equipment, structural parts, agricultural machinery, household goods, and the like.
With the increasing expansion of the application field of POM, the performance requirements on all aspects of POM are higher and higher. Because the oxygen index of POM is 14.9%, the POM is a combustible plastic, has a melt dripping phenomenon, cannot meet the field with high requirement on flame retardant property, and greatly limits the application range of the POM, the POM needs to be subjected to flame retardant modification. The development of the flame-retardant polyformaldehyde with excellent comprehensive performance has important significance for expanding the application range of the POM.
At present, the flame retardant performance of the flame-retardant POM is mainly realized by adding a flame retardant. However, POM is very demanding on flame retardants during molding and processing, and some additives can not retard POM, but rather accelerate its decomposition. It is reported that the Intumescent Flame Retardant (IFR) has a certain flame retardant effect on POM, and has attracted attention due to its excellent flame retardant properties such as no halogen, low toxicity, no corrosive gas generation, etc.
The organic phosphorus flame retardant is a new and elegant material in modern flame retardants, is also an important component of IFR, and overcomes the defect that the traditional halogen flame retardant is decomposed to release toxic gas. Among them, 9, 10-dihydro-9-oxa-10-phenanthrene-10-oxide (DOPO) and its derivatives have biphenyl, phenanthrene ring, and O ═ P-O structures in the structure, so that they have the advantages of migration resistance, good flame retardant properties, and the like, and thus they are the research hotspots of phosphorus flame retardants.
In view of the above situation, research and development personnel have focused on the development and compounding work of organophosphorus flame retardants in the research of flame-retardant POM, so as to solve the flame-retardant problem in the use process of POM.
Disclosure of Invention
Aiming at the problems of small selectivity, poor flame retardant effect and single function of the flame retardant for polyformaldehyde in the prior art, the invention aims to provide the novel special flame retardant for polyformaldehyde, which is reasonable in formula, has high-efficiency flame retardance, and also has high-efficiency ultraviolet absorption performance and heat resistance.
The second purpose of the invention is to provide a preparation method capable of quickly preparing the novel special polyformaldehyde flame retardant.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a novel special flame retardant for polyformaldehyde has the following structural formula:
a method for preparing the novel special flame retardant for polyoxymethylene as claimed in claim 1, which comprises the following steps:
(1) adding cyanuric chloride, 2, 4-dihydroxy benzene boric acid, a palladium catalyst and alkali into a flask for mixing, then adding toluene, heating to 80-110 ℃, stirring for reaction for 1-6 h, cooling to room temperature, pouring a mixed solution of dichloromethane and deionized water into a reaction solution for washing, extracting, separating liquid, washing a water phase with dichloromethane, combining organic phases, drying with anhydrous sodium sulfate, concentrating in vacuum, and separating and purifying by silica gel column chromatography to obtain an intermediate product I; wherein, the developing solvent used for the separation and purification is petroleum ether: dichloromethane ═ 3: 1; the dosage ratio of the cyanuric chloride, the 2, 4-dihydroxy benzene boric acid, the palladium catalyst, the alkali and the toluene is as follows: 1 mol: 4.0-5.0 mol: 5mol percent: 10 mol: 10L; the volume ratio of the dichloromethane to the deionized water in the mixed solution is as follows: 1: 1; the dosage ratio of the toluene, the mixed solution and the dichloromethane is as follows: 10L: 20L: 20L;
(2) adding the intermediate product I, allyl bromide and potassium carbonate into DMF, heating to 100-130 ℃, stirring for 1-3 h, cooling and standing to obtain a solution; then carrying out vacuum concentration on the solution, and enriching residual components; adding deionized water, stirring for about 30min, adding dichloromethane, stirring for about 30min, standing for layering, drying the organic phase, filtering, and rotary steaming to obtain intermediate product II; wherein the dosage ratio of the intermediate product I, allyl bromide, potassium carbonate and DMF is as follows: 1 mol: 3.0-3.5 mol: 3.0-3.5 mol: 0.5L; the dosage ratio of DMF, deionized water and dichloromethane is as follows: 0.5L: 0.5L: 0.6L;
(3) and (3) dissolving the intermediate product II and DOPO in DMF, adding AIBN, carrying out oil bath at 70-80 ℃ for 8-10 h, carrying out reduced pressure distillation after the reaction is finished, dissolving in dichloromethane, washing to be neutral, separating liquid, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain a target product III. Wherein the dosage ratio of the intermediate product II, DOPO and DMF is as follows: 1 mol: 3.0-4.0 mol: 0.5L; the dosage ratio of the AIBN to the intermediate product II is as follows: 100g of 1.0-2.0 g; the dosage ratio of DMF, dichloromethane, sodium hydroxide aqueous solution and deionized water is as follows: 0.5L: 0.5L: 0.6L: 0.6L.
In a preferred embodiment of the present invention, the palladium catalyst is preferably palladium acetate triphenylphosphine. The base is preferably potassium carbonate or sodium hydroxide.
The preparation process of the invention is as follows:
the invention has the beneficial effects that: the flame retardant is reasonable in formula, and is prepared by taking cyanuric chloride, 2, 4-dihydroxy benzene boric acid, allyl bromide and DOPO as raw materials and reacting through the steps of coupling, substitution and addition; the three-molecule reaction type flame retardant DOPO is a novel expansion type nitrogen-phosphorus flame retardant which integrates an acid source, a carbon source and a gas source into a whole, has high N content, a hydroxyl structure, a polycyclic structure capable of forming a stable carbonization layer and the like; the ultraviolet light absorber contains a triazine structure, and triazine is an ultraviolet light absorber with high efficiency, low color, high processing temperature, good compatibility and excellent broad spectrum property (strong absorption of 300-380nm wavelength), so that the base material can be endowed with excellent light aging resistance, and the service life of the material is prolonged; and more benzene rings and six-membered rings exist, so that the heat resistance and the mechanical strength of the polyformaldehyde can be obvious, and the synergistic effect of improving the light aging resistance and the flame retardance is achieved. The novel special polyformaldehyde flame retardant disclosed by the invention has high-efficiency flame retardance, high-efficiency ultraviolet absorption performance and heat resistance, and is particularly suitable for the fields of outdoor building decoration and the like.
The present invention will be described in detail with reference to examples. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.
Detailed Description
Example 1: a preparation method of a novel special flame retardant for polyformaldehyde comprises the following steps:
(1) adding cyanuric chloride, 2, 4-dihydroxy benzene boric acid, palladium acetate triphenylphosphine and potassium carbonate into a flask, adding toluene, heating to 80 ℃, and stirring to react for 6 hours; cooling to room temperature, pouring a mixed solution of dichloromethane and deionized water into the reaction solution for washing, extracting, separating liquid, washing a water phase by using dichloromethane, combining organic phases, drying by using anhydrous sodium sulfate, concentrating in vacuum, and separating and purifying by using silica gel column chromatography, wherein a developing agent is petroleum ether: dichloromethane ═ 3:1 to give intermediate I;
the infrared data are as follows: 3511cm-1: -OH is present; 1511cm-1: a triazine ring is present; 742cm-1: -C-Cl disappearance;
wherein the dosage ratio of the cyanuric chloride, the 2, 4-dihydroxy benzene boric acid, the palladium acetate triphenylphosphine, the potassium carbonate and the toluene is as follows: 1 mol: 5.0 mol: 5mol percent: 10 mol: 10L; the volume ratio of the dichloromethane to the deionized water in the mixed solution is as follows: 1: 1; the dosage ratio of the toluene, the mixed solution and the dichloromethane is as follows: 10L: 20L: 20L;
(2) adding the intermediate product I, allyl bromide and potassium carbonate into DMF, heating to 120 ℃, stirring strongly for 3h, cooling, standing, and concentrating the solution in vacuum to enrich the residual components; slowly adding deionized water, stirring for 30min, adding dichloromethane, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain intermediate product II;
the infrared data are as follows: 3511cm-1: -OH is present; 1614cm-1: -C ═ C-is present; 1511cm-1: a triazine ring is present; 696cm-1: -C-Br disappearance;
wherein the dosage ratio of the intermediate product I, allyl bromide, potassium carbonate and DMF is as follows: 1 mol: 3.5 mol: 3.5 mol: 0.5L; the dosage ratio of DMF, deionized water and dichloromethane is as follows: 0.5L: 0.5L: 0.6L;
(3) dissolving the intermediate product II and DOPO in DMF, adding AIBN, carrying out oil bath at 70 ℃ for 10h, carrying out reduced pressure distillation after the reaction is finished, dissolving in dichloromethane, washing for 3 times by using 1M sodium hydroxide aqueous solution and deionized water respectively until the solution is neutral, carrying out liquid separation, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain a target product III;
the infrared data are as follows: 3511cm-1: -OH is present; 1614cm-1: -C ═ C — disappearance; 1511cm-1: a triazine ring is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH-is present; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present;
the nuclear magnetic hydrogen spectrum data is as follows:1H NMR(400MHz，CDCl3δ ppm): 7.0-8.6(33H, benzene ring); 4.06(6H, -CH)2-)；1.25(6H，-CH2-)；3.25(6H，-CH2-)；9.83(3H，-OH)。
Wherein the dosage ratio of the intermediate product II, DOPO and DMF is as follows: 1 mol: 3.5 mol: 0.5L; the dosage ratio of the AIBN to the intermediate product II is as follows: 1.5g to 100 g; the dosage ratio of DMF, dichloromethane, sodium hydroxide aqueous solution and deionized water is as follows: 0.5L: 0.5L: 0.6L: 0.6L.
Example 2: a preparation method of a novel special flame retardant for polyformaldehyde comprises the following steps:
(1) adding cyanuric chloride, 2, 4-dihydroxy benzene boric acid, palladium acetate triphenylphosphine and potassium carbonate into a flask, adding toluene, heating to 80 ℃, and stirring for reacting for 4 hours; cooling to room temperature, pouring a mixed solution of dichloromethane and deionized water into the reaction solution for washing, extracting, separating liquid, washing a water phase by using dichloromethane, combining organic phases, drying by using anhydrous sodium sulfate, concentrating in vacuum, and separating and purifying by using silica gel column chromatography, wherein a developing agent is petroleum ether: dichloromethane ═ 3:1 to give intermediate I;
the infrared data are as follows: 3511cm-1: -OH is present; 1511cm-1: a triazine ring is present; 742cm-1: -C-Cl disappearance;
wherein the dosage ratio of the cyanuric chloride, the 2, 4-dihydroxy benzene boric acid, the palladium acetate triphenylphosphine, the potassium carbonate and the toluene is as follows: 1 mol: 4.5 mol: 5mol percent: 10 mol: 10L; the volume ratio of the dichloromethane to the deionized water in the mixed solution is as follows: 1: 1; the dosage ratio of the toluene, the mixed solution and the dichloromethane is as follows: 10L: 20L: 20L;
(2) adding the intermediate product I, allyl bromide and potassium carbonate into DMF, heating to 120 ℃, stirring strongly for 2h, cooling, standing, and concentrating the solution in vacuum to enrich the residual components; slowly adding deionized water, stirring for 30min, adding dichloromethane, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain intermediate product II;
the infrared data are as follows: 3511cm-1: -OH is present; 1614cm-1: -C ═ C-is present; 1511cm-1: a triazine ring is present; 696cm-1: -C-Br disappearance;
wherein the dosage ratio of the intermediate product I, allyl bromide, potassium carbonate and DMF is as follows: 1 mol: 3.0 mol: 3.0 mol: 0.5L; the dosage ratio of DMF, deionized water and dichloromethane is as follows: 0.5L: 0.5L: 0.6L;
(3) dissolving the intermediate product II and DOPO in DMF, adding AIBN, carrying out oil bath at 80 ℃ for 8h, carrying out reduced pressure distillation after the reaction is finished, dissolving in dichloromethane, washing for 3 times by using 1M sodium hydroxide aqueous solution and deionized water respectively until the solution is neutral, carrying out liquid separation, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain a target product III;
the infrared data are as follows: 3511cm-1: -OH is present; 1614cm-1: -C ═ C — disappearance; 1511cm-1: a triazine ring is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH-is present; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present;
the nuclear magnetic hydrogen spectrum data is as follows:1H NMR(400MHz，CDCl3δ ppm): 7.0-8.6(33H, benzene ring); 4.06(6H, -CH)2-)；1.25(6H，-CH2-)；3.25(6H，-CH2-)；9.83(3H，-OH)。
Wherein the dosage ratio of the intermediate product II, DOPO and DMF is as follows: 1 mol: 3.0 mol: 0.5L; the dosage ratio of the AIBN to the intermediate product II is as follows: 1.0g to 100 g; the dosage ratio of DMF, dichloromethane, sodium hydroxide aqueous solution and deionized water is as follows: 0.5L: 0.5L: 0.6L: 0.6L;
example 3: a preparation method of a novel special flame retardant for polyformaldehyde comprises the following steps:
(1) adding cyanuric chloride, 2, 4-dihydroxy benzene boric acid, palladium acetate triphenylphosphine and sodium hydroxide into a flask, adding toluene, heating to 80 ℃, stirring and reacting for 5 hours; cooling to room temperature, pouring a mixed solution of dichloromethane and deionized water into the reaction solution for washing, extracting, separating liquid, washing a water phase by using dichloromethane, combining organic phases, drying by using anhydrous sodium sulfate, concentrating in vacuum, and separating and purifying by using silica gel column chromatography, wherein a developing agent is petroleum ether: dichloromethane ═ 3:1 to give intermediate I;
the infrared data are as follows: 3511cm-1: -OH is present; 1511cm-1: a triazine ring is present; 742cm-1: -C-Cl disappearance;
wherein the dosage ratio of the cyanuric chloride, the 2, 4-dihydroxy benzene boric acid, the palladium acetate triphenylphosphine, the sodium hydroxide and the toluene is as follows: 1 mol: 4.0 mol: 5mol percent: 10 mol: 10L; the volume ratio of the dichloromethane to the deionized water in the mixed solution is as follows: 1: 1; the dosage ratio of the toluene, the mixed solution and the dichloromethane is as follows: 10L: 20L: 20L;
(2) adding the intermediate product I, allyl bromide and potassium carbonate into DMF, heating to 130 ℃, stirring strongly for 1h, cooling, standing, and concentrating the solution in vacuum to enrich the residual components; slowly adding deionized water, stirring for 30min, adding dichloromethane, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain intermediate product II;
the infrared data are as follows: 3511cm-1: -OH is present; 1614cm-1: -C ═ C-is present; 1511cm-1: a triazine ring is present; 696cm-1: -C-Br disappearance;
wherein the dosage ratio of the intermediate product I, allyl bromide, potassium carbonate and DMF is as follows: 1 mol: 3.2 mol: 3.2 mol: 0.5L; the dosage ratio of DMF, deionized water and dichloromethane is as follows: 0.5L: 0.5L: 0.6L;
(3) dissolving the intermediate product II and DOPO in DMF, adding AIBN, carrying out oil bath at 75 ℃ for 8h, carrying out reduced pressure distillation after the reaction is finished, dissolving in dichloromethane, washing for 3 times by using 1M sodium hydroxide aqueous solution and deionized water respectively until the solution is neutral, carrying out liquid separation, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain a target product III;
the infrared data are as follows: 3511cm-1: -OH is present; 1614cm-1: -C ═ C — disappearance; 1511cm-1: a triazine ring is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH-is present; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present;
the nuclear magnetic hydrogen spectrum data is as follows:1H NMR(400MHz，CDCl3δ ppm): 7.0-8.6(33H, benzene ring); 4.06(6H, -CH)2-)；1.25(6H，-CH2-)；3.25(6H，-CH2-)；9.83(3H，-OH)；
Wherein the dosage ratio of the intermediate product II, DOPO and DMF is as follows: 1 mol: 4.0 mol: 0.5L; the dosage ratio of the AIBN to the intermediate product II is as follows: 2.0g to 100 g; the dosage ratio of DMF, dichloromethane, sodium hydroxide aqueous solution and deionized water is as follows: 0.5L: 0.5L: 0.6L: 0.6L;
example 4: a preparation method of a novel special flame retardant for polyformaldehyde comprises the following steps:
(1) adding cyanuric chloride, 2, 4-dihydroxy benzene boric acid, palladium acetate triphenylphosphine and potassium carbonate into a flask, adding toluene, heating to 110 ℃, stirring and reacting for 1 h; cooling to room temperature, pouring a mixed solution of dichloromethane and deionized water into the reaction solution for washing, extracting, separating liquid, washing a water phase by using dichloromethane, combining organic phases, drying by using anhydrous sodium sulfate, concentrating in vacuum, and separating and purifying by using silica gel column chromatography, wherein a developing agent is petroleum ether: dichloromethane ═ 3:1 to give intermediate I;
the infrared data are as follows: 3511cm-1: -OH is present; 1511cm-1: a triazine ring is present; 742cm-1: -C-Cl disappearance;
wherein the dosage ratio of the cyanuric chloride, the 2, 4-dihydroxy benzene boric acid, the palladium acetate triphenylphosphine, the potassium carbonate and the toluene is as follows: 1 mol: 4.5 mol: 5mol percent: 10 mol: 10L; the volume ratio of the dichloromethane to the deionized water in the mixed solution is as follows: 1: 1; the dosage ratio of the toluene, the mixed solution and the dichloromethane is as follows: 10L: 20L: 20L;
(2) adding the intermediate product I, allyl bromide and potassium carbonate into DMF, heating to 110 ℃, stirring strongly for 2h, cooling, standing, and concentrating the solution in vacuum to enrich the residual components; slowly adding deionized water, stirring for 30min, adding dichloromethane, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain intermediate product II;
the infrared data are as follows: 3511cm-1: -OH is present; 1614cm-1: -C ═ C-is present; 1511cm-1: a triazine ring is present; 696cm-1: -C-Br disappearance;
wherein the dosage ratio of the intermediate product I, allyl bromide, potassium carbonate and DMF is as follows: 1 mol: 3.4 mol: 3.4 mol: 0.5L; the dosage ratio of DMF, deionized water and dichloromethane is as follows: 0.5L: 0.5L: 0.6L;
(3) dissolving the intermediate product II and DOPO in DMF, adding AIBN, carrying out oil bath at 70 ℃ for 9h, carrying out reduced pressure distillation after the reaction is finished, dissolving in dichloromethane, washing for 3 times by using 1M sodium hydroxide aqueous solution and deionized water respectively until the solution is neutral, carrying out liquid separation, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain a target product III;
the infrared data are as follows: 3511cm-1: -OH is present; 1614cm-1: -C ═ C — disappearance; 1511cm-1: a triazine ring is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: in P-CH-groupC-H exists; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present;
the nuclear magnetic hydrogen spectrum data is as follows:1H NMR(400MHz，CDCl3δ ppm): 7.0-8.6(33H, benzene ring); 4.06(6H, -CH)2-)；1.25(6H，-CH2-)；3.25(6H，-CH2-)；9.83(3H，-OH)；
Wherein the dosage ratio of the intermediate product II, DOPO and DMF is as follows: 1 mol: 4.0 mol: 0.5L; the dosage ratio of the AIBN to the intermediate product II is as follows: 1.0g to 100 g; the dosage ratio of DMF, dichloromethane, sodium hydroxide aqueous solution and deionized water is as follows: 0.5L: 0.5L: 0.6L: 0.6L;
example 5: a preparation method of a novel special flame retardant for polyformaldehyde comprises the following steps:
(1) adding cyanuric chloride, 2, 4-dihydroxy benzene boric acid, palladium acetate triphenylphosphine and potassium carbonate into a flask, adding toluene, heating to 90 ℃, stirring and reacting for 3 hours; cooling to room temperature, pouring a mixed solution of dichloromethane and deionized water into the reaction solution for washing, extracting, separating liquid, washing a water phase by using dichloromethane, combining organic phases, drying by using anhydrous sodium sulfate, concentrating in vacuum, and separating and purifying by using silica gel column chromatography, wherein a developing agent is petroleum ether: dichloromethane ═ 3:1 to give intermediate I;
the infrared data are as follows: 3511cm-1: -OH is present; 1511cm-1: a triazine ring is present; 742cm-1: -C-Cl disappearance;
wherein the dosage ratio of the cyanuric chloride, the 2, 4-dihydroxy benzene boric acid, the palladium acetate triphenylphosphine, the potassium carbonate and the toluene is as follows: 1 mol: 5.0 mol: 5mol percent: 10 mol: 10L; the volume ratio of the dichloromethane to the deionized water in the mixed solution is as follows: 1: 1; the dosage ratio of the toluene, the mixed solution and the dichloromethane is as follows: 10L: 20L: 20L;
(2) adding the intermediate product I, allyl bromide and potassium carbonate into DMF, heating to 100 ℃, stirring strongly for 2h, cooling, standing, and concentrating the solution in vacuum to enrich the residual components; slowly adding deionized water, stirring for 30min, adding dichloromethane, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain intermediate product II;
the infrared data are as follows: 3511cm-1: -OH is present; 1614cm-1: -C ═ C-is present; 1511cm-1: a triazine ring is present; 696cm-1: -C-Br disappearance;
wherein the dosage ratio of the intermediate product I, allyl bromide, potassium carbonate and DMF is as follows: 1 mol: 3.5 mol: 3.5 mol: 0.5L; the dosage ratio of DMF, deionized water and dichloromethane is as follows: 0.5L: 0.5L: 0.6L;
(3) dissolving the intermediate product II and DOPO in DMF, adding AIBN, performing oil bath at 80 ℃ for 10h, performing reduced pressure distillation after the reaction is finished, dissolving in dichloromethane, washing for 3 times by using 1M sodium hydroxide aqueous solution and deionized water respectively until the solution is neutral, separating the solution, taking an organic phase, performing reduced pressure distillation, and performing vacuum drying to obtain a target product III;
the infrared data are as follows: 3511cm-1: -OH is present; 1614cm-1: -C ═ C — disappearance; 1511cm-1: a triazine ring is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH-is present; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present;
the nuclear magnetic hydrogen spectrum data is as follows:1H NMR(400MHz，CDCl3δ ppm): 7.0-8.6(33H, benzene ring); 4.06(6H, -CH)2-)；1.25(6H，-CH2-)；3.25(6H，-CH2-)；9.83(3H，-OH)；
Wherein the dosage ratio of the intermediate product II, DOPO and DMF is as follows: 1 mol: 3.5 mol: 0.5L; the dosage ratio of the AIBN to the intermediate product II is as follows: 1.0g to 100 g; the dosage ratio of DMF, dichloromethane, sodium hydroxide aqueous solution and deionized water is as follows: 0.5L: 0.5L: 0.6L: 0.6L;
example 6: a preparation method of a novel special flame retardant for polyformaldehyde comprises the following steps:
(1) adding cyanuric chloride, 2, 4-dihydroxy benzene boric acid, palladium acetate triphenylphosphine and potassium carbonate into a flask, adding toluene, heating to 100 ℃, stirring and reacting for 2 hours; cooling to room temperature, pouring a mixed solution of dichloromethane and deionized water into the reaction solution for washing, extracting, separating liquid, washing a water phase by using dichloromethane, combining organic phases, drying by using anhydrous sodium sulfate, concentrating in vacuum, and separating and purifying by using silica gel column chromatography, wherein a developing agent is petroleum ether: dichloromethane ═ 3:1 to give intermediate I;
the infrared data are as follows: 3511cm-1: -OH is present; 1511cm-1: a triazine ring is present; 742cm-1: -C-Cl disappearance;
wherein the dosage ratio of the cyanuric chloride, the 2, 4-dihydroxy benzene boric acid, the palladium acetate triphenylphosphine, the potassium carbonate and the toluene is as follows: 1 mol: 5.0 mol: 5mol percent: 10 mol: 10L; the volume ratio of the dichloromethane to the deionized water in the mixed solution is as follows: 1: 1; the dosage ratio of the toluene, the mixed solution and the dichloromethane is as follows: 10L: 20L: 20L;
(2) adding the intermediate product I, allyl bromide and potassium carbonate into DMF, heating to 110 ℃, stirring strongly for 3h, cooling, standing, and concentrating the solution in vacuum to enrich the residual components; slowly adding deionized water, stirring for 30min, adding dichloromethane, stirring for 30min, standing for layering, drying the organic phase with anhydrous sodium sulfate, filtering, and rotary steaming to obtain intermediate product II;
the infrared data are as follows: 3511cm-1: -OH is present; 1614cm-1: -C ═ C-is present; 1511cm-1: a triazine ring is present; 696cm-1: -C-Br disappearance;
wherein the dosage ratio of the intermediate product I, allyl bromide, potassium carbonate and DMF is as follows: 1 mol: 3.5 mol: 3.5 mol: 0.5L; the dosage ratio of DMF, deionized water and dichloromethane is as follows: 0.5L: 0.5L: 0.6L;
(3) dissolving the intermediate product II and DOPO in DMF, adding AIBN, carrying out oil bath at 75 ℃ for 9h, carrying out reduced pressure distillation after the reaction is finished, dissolving in dichloromethane, washing for 3 times by using 1M sodium hydroxide aqueous solution and deionized water respectively until the solution is neutral, carrying out liquid separation, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain a target product III;
the infrared data are as follows: 3511cm-1: -OH is present; 1614cm-1: -C ═ C — disappearance; 1511cm-1: a triazine ring is present; 3064cm-1: a benzene ring-C-H exists; 2920cm-1: C-H in P-CH-is present; 1593cm-1、1544cm-1: a benzene ring is present; 1302cm-1: p ═ O present; 1190cm-1: P-O-is present;
the nuclear magnetic hydrogen spectrum data is as follows:1H NMR(400MHz，CDCl3δ ppm): 7.0-8.6(33H, benzene ring); 4.06(6H, -CH)2-)；1.25(6H，-CH2-)；3.25(6H，-CH2-)；9.83(3H，-OH)；
Wherein the dosage ratio of the intermediate product II, DOPO and DMF is as follows: 1 mol: 3.5 mol: 0.5L; the dosage ratio of the AIBN to the intermediate product II is as follows: 1.5g to 100 g; the dosage ratio of DMF, dichloromethane, sodium hydroxide aqueous solution and deionized water is as follows: 0.5L: 0.5L: 0.6L: 0.6L;
the novel special flame retardant for polyformaldehyde obtained in the embodiment 1 is used as a base material of an application embodiment, and is prepared into a flame-retardant polyformaldehyde material.
Application example 1: the flame-retardant polyformaldehyde comprises the following raw materials in parts by weight: 70 parts of POM; 15 parts of ammonium polyphosphate; 7.5 parts of melamine; 5.5 parts of pentaerythritol; 2 parts of a target product III; 10100.2 parts of an antioxidant; 1680.2 parts of antioxidant.
Application example 2: the flame-retardant polyformaldehyde comprises the following raw materials in parts by weight: 70 parts of POM; 16 parts of ammonium polyphosphate; 7.5 parts of melamine; 5.5 parts of pentaerythritol; 1 part of a target product III; 10100.2 parts of an antioxidant; 1680.2 parts of antioxidant.
Application example 3: the flame-retardant polyformaldehyde comprises the following raw materials in parts by weight: 70 parts of POM; 14 parts of ammonium polyphosphate; 7.5 parts of melamine; 5.5 parts of pentaerythritol; 3 parts of a target product III; 10100.2 parts of an antioxidant; 1680.2 parts of antioxidant.
Application example 4: the flame-retardant polyformaldehyde comprises the following raw materials in parts by weight: 70 parts of POM; 13 parts of ammonium polyphosphate; 7.5 parts of melamine; 5.5 parts of pentaerythritol; 4 parts of a target product III; 10100.2 parts of an antioxidant; 1680.2 parts of antioxidant.
Application example 5: the flame-retardant polyformaldehyde comprises the following raw materials in parts by weight: 70 parts of POM; 15 parts of ammonium polyphosphate; 8 parts of melamine; 5 parts of pentaerythritol; 2 parts of a target product III; 10100.2 parts of an antioxidant; 1680.2 parts of antioxidant.
Application example 6: the flame-retardant polyformaldehyde comprises the following raw materials in parts by weight: 70 parts of POM; 15 parts of ammonium polyphosphate; 6 parts of melamine; 7 parts of pentaerythritol; 2 parts of a target product III; 10100.2 parts of an antioxidant; 1680.2 parts of antioxidant.
Application example 7: the flame-retardant polyformaldehyde comprises the following raw materials in parts by weight: 70 parts of POM; 15 parts of ammonium polyphosphate; 7 parts of melamine; 6 parts of pentaerythritol; 2 parts of a target product III; 10100.2 parts of an antioxidant; 1680.2 parts of antioxidant.
Use of the flame-retardant polyoxymethylenes of comparative examples 1 to 7 in comparison with application example 1:
application example comparative example 1: the flame-retardant polyformaldehyde comprises the following raw materials in parts by weight: 70 parts of POM; 10100.2 parts of an antioxidant; 1680.2 parts of antioxidant.
Application example comparative example 2: the flame-retardant polyformaldehyde comprises the following raw materials in parts by weight: 70 parts of POM; 16 parts of ammonium polyphosphate; 8 parts of melamine; 6 parts of pentaerythritol; 10100.2 parts of an antioxidant; 1680.2 parts of antioxidant.
Application example comparative example 3: the flame-retardant polyformaldehyde comprises the following raw materials in parts by weight: 70 parts of POM; 15 parts of ammonium polyphosphate; 7.5 parts of melamine; 5.5 parts of pentaerythritol; 2 parts of DOPO; 10100.2 parts of an antioxidant; 1680.2 parts of antioxidant.
Application example comparative example 4: the flame-retardant polyformaldehyde comprises the following raw materials in parts by weight: 70 parts of POM; 15 parts of ammonium polyphosphate; 7.5 parts of melamine; 5.5 parts of pentaerythritol; UV-52 parts; 10100.2 parts of an antioxidant; 1680.2 parts of antioxidant.
The preparation method of the flame-retardant polyformaldehyde of the application examples 1-7 and the application examples 1-4 comprises the following steps: the method comprises the following steps:
POM is firstly put into a drying oven, dried for 4 hours at the temperature of 80 ℃, accurately weighed according to the formula and uniformly mixed in a high-speed mixer. And after the mixing is finished, adding the mixture into a set double-screw extruder, melting, blending and extruding the mixture by using the double-screw extruder, cooling the mixture by using a water tank to reduce the temperature of the POM to be below Tg, and drawing and granulating the mixture to obtain the flame-retardant modified polyformaldehyde particles.
The parameters of the extruder are as follows: a first area: 185 ℃ and a second zone: 190 ℃ and three zones: 190 ℃ and head temperature: 185 ℃ and the main engine rotating speed: 600rpm, feeding voltage: 40V, pelletizing speed: 350 rpm.
The physical properties, including flame retardancy, mechanical properties, thermal properties, etc., of the flame-retardant polyoxymethylene prepared in practical examples 1 to 7 of the present invention and practical examples 1 to 4 were measured, respectively, and the results are shown in table 1.
TABLE 1
Firstly, as can be seen from table 1, the novel flame retardant for POM of the present invention can effectively improve the adverse effect of the conventional flame retardant on mechanical properties when used in combination with other conventional flame retardants.
Secondly, compared with the conventional low-toxicity flame retardant DOPO, the novel flame retardant disclosed by the invention has the advantages of obvious flame retardant advantage and obvious improvement on the limiting oxygen index, and belongs to a flame-retardant material.
Thirdly, the novel flame retardant disclosed by the invention has excellent UV resistance, and the ultraviolet blocking efficiency of the novel flame retardant is superior to that of a common triazine ultraviolet absorbent.
Fourthly, the novel flame retardant disclosed by the invention has an obvious advantage in improving the thermal stability of the flame-retardant POM material.
In conclusion, compared with the conventional common flame retardant, the novel flame retardant for PP disclosed by the invention not only solves the problems of poor flame retardant effect, single function and the like of the conventional composite flame retardant, has obvious advantages in flame retardant effect, but also has high-efficiency light stability and thermal stability, does not influence the final mechanical property of the material, and even can generate favorable effects on the mechanical property. The test method comprises the following steps:
(1) and (3) molten drop test: measured using a horizontal vertical burning tester (UL-94).
(2) Limiting oxygen index: the flame retardancy was tested with reference to GB 8624 and 2012.
(3) Residual carbon content: a thermogravimetric analyzer is used, nitrogen protection is carried out, and the temperature rising speed is 10 ℃/min.
(4) Ultraviolet blocking efficiency: the ultraviolet visible spectrometer tests the transmittance of the material at 200-400nm, and the lower the transmittance, the higher the blocking efficiency, i.e. the better the UV resistance. The ultraviolet blocking efficiency expression method comprises the following steps: 5 is optimal and 1 is worst.
(5) Mechanical properties: according to GB/T1040-. The dimensions of the standard dumbbell-shaped tensile bars are 150mm × 10mm × 4mm, the gauge length is 50mm, the tensile rate is 50mm/min, and the average of 5 specimens is taken for each sample.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. Other flame retardants obtained by the same or similar methods and compositions as those described in the above examples of the present invention and methods for their preparation are within the scope of the present invention.
Claims (10)
1. A novel special flame retardant for polyformaldehyde is characterized in that the structural formula is as follows:
2. a preparation method of the novel special flame retardant for polyoxymethylene, according to claim 1, is characterized in that: which comprises the following steps:
(1) mixing cyanuric chloride, 2, 4-dihydroxy benzene boric acid, a palladium catalyst and an alkali phase, then adding toluene, heating and stirring, cooling to room temperature after reaction is finished, pouring a mixed solution of dichloromethane and deionized water into a reaction solution, washing, extracting, separating, washing a water phase by dichloromethane, combining organic phases, drying, concentrating in vacuum, and separating and purifying by silica gel column chromatography to obtain an intermediate product I;
(2) adding the intermediate product I, allyl bromide and potassium carbonate into DMF, heating and stirring, cooling and standing to obtain a solution; then carrying out vacuum concentration on the solution, and enriching residual components; adding deionized water, stirring, adding dichloromethane, stirring, standing for layering, drying the organic phase, filtering, and rotary steaming to obtain intermediate product II;
(3) and (3) dissolving the intermediate product II and DOPO in DMF, adding AIBN, carrying out oil bath at 70-80 ℃ for 8-10 h, carrying out reduced pressure distillation after the reaction is finished, dissolving in dichloromethane, washing to be neutral, separating liquid, taking an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain a target product III.
3. The preparation method of the novel special flame retardant for polyoxymethylene according to claim 2, wherein: and (2) adding toluene in the step (1), heating to 80-110 ℃, stirring for reaction for 1-6 h, and cooling to room temperature.
4. The preparation method of the novel special flame retardant for polyoxymethylene according to claim 2, wherein: the dosage ratio of the cyanuric chloride, the 2, 4-dihydroxy benzene boric acid, the palladium catalyst, the alkali and the toluene is as follows: 1 mol: 4.0-5.0 mol: 5mol percent: 10 mol: 10L; the volume ratio of the dichloromethane to the deionized water in the mixed solution is as follows: 1: 1; the dosage ratio of the toluene, the mixed solution and the dichloromethane is as follows: 10L: 20L: 20L.
5. The preparation method of the novel special flame retardant for polyoxymethylene according to claim 2, wherein: and (2) adding the intermediate product I, allyl bromide and potassium carbonate into DMF, heating to 100-130 ℃, stirring for 1-3 h, cooling and standing.
6. The preparation method of the novel special flame retardant for polyoxymethylene according to claim 2, wherein: the dosage ratio of the intermediate product I, allyl bromide, potassium carbonate and DMF is as follows: 1 mol: 3.0-3.5 mol: 3.0-3.5 mol: 0.5L; the dosage ratio of DMF, deionized water and dichloromethane is as follows: 0.5L: 0.5L: 0.6L.
7. The preparation method of the novel special flame retardant for polyoxymethylene according to claim 2, wherein: the dosage ratio of the intermediate product II, DOPO and DMF is as follows: 1 mol: 3.0-4.0 mol: 0.5L; the dosage ratio of the AIBN to the intermediate product II is as follows: 100g of 1.0-2.0 g; the dosage ratio of DMF, dichloromethane, sodium hydroxide aqueous solution and deionized water is as follows: 0.5L: 0.5L: 0.6L: 0.6L.
8. The preparation method of the novel special flame retardant for polyoxymethylene according to claim 2, wherein: the palladium catalyst is palladium acetate triphenylphosphine.
9. The preparation method of the novel special flame retardant for polyoxymethylene according to claim 2, wherein: the alkali is potassium carbonate or sodium hydroxide.
10. The preparation method of the novel special flame retardant for polyoxymethylene according to claim 2, wherein: the developing solvent used for separation and purification in the step (1) is petroleum ether: dichloromethane ═ 3: 1.
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