CN104277223B - Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant - Google Patents
Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant Download PDFInfo
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- CN104277223B CN104277223B CN201310292269.7A CN201310292269A CN104277223B CN 104277223 B CN104277223 B CN 104277223B CN 201310292269 A CN201310292269 A CN 201310292269A CN 104277223 B CN104277223 B CN 104277223B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 44
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 22
- 239000011574 phosphorus Substances 0.000 title claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 20
- 239000010703 silicon Substances 0.000 title claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 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 abstract description 31
- 238000001308 synthesis method Methods 0.000 title abstract 3
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 4
- 229920006351 engineering plastic Polymers 0.000 claims abstract description 4
- 239000003822 epoxy resin Substances 0.000 claims abstract description 4
- 229920001558 organosilicon polymer Polymers 0.000 claims abstract description 4
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 4
- 239000004677 Nylon Substances 0.000 claims abstract description 3
- 229920001778 nylon Polymers 0.000 claims abstract description 3
- 229920002635 polyurethane Polymers 0.000 claims abstract description 3
- 239000004814 polyurethane Substances 0.000 claims abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 125000001624 naphthyl group Chemical class 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- -1 C6-C22Aryl Chemical group 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 abstract 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 abstract 1
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 125000003277 amino group Chemical group 0.000 abstract 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 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 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and a synthesis method of the macromolecular flame retardant. The synthesis method is characterized in that an organic silicon polymer containing an amino group firstly reacts with an aldehyde type substance and then reacts with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to prepare novel flame retardant molecules which simultaneously contain three flame retardant elements of phosphorus, nitrogen and silicon in the molecules. The flame retardant disclosed by the invention is simple in a preparation process and has good solubility with resin, and the three flame retardant elements of phosphorus, nitrogen and silicon are synergistic for realizing flame retardance, so that the flame retardant effect of resin added with the flame retardant is significantly improved, and the flame retardant can be used as the additive flame retardant for halogen-free flame retardance of epoxy resin, polyurethane, ABS (acrylonitrile butadiene styrene), nylon and other engineering plastics.
Description
Technical field
The present invention relates to not halogen-containing fire retardant of a class and preparation method thereof, belong to Minute Organic Synthesis technical field.
Background technology
With the progress of industrial technology, increasing organic synthesis macromolecular material enters into our daily life
In, these materials have excellent properties, as good in hardness, and tensile strength is high, and water-fast, corrosion-resistant etc., range is very wide.But by
It is all inflammable or combustible in epoxy resin, polyester and engineering plastics Polymer material great majority, and release when burning
Substantial amounts of poisonous and corrosive gas, so the harmfulness that the fire being induced by produces is also more serious.Therefore prevent height
The fire that molecular material burning causes has become as people needs the urgent problem solving.
At present, use halogenated flame retardant although halogenated flame retardant flame retardant effect is preferable in macromolecular material more, but such
Fire retardant often decomposes generation toxic gas when meeting fire burning(As HBr), or even produce many bromos dibenzo two in burning
The carcinogen such as English and PBDF is restricted so using.Organophosphorous fire retardant is considered as to replace
The organic fire-retardant of halogen flame, this based flame retardant is mostly nontoxic, low cigarette and flame retardant effect substantially, wherein organophosphorus ester
Class product is more, but organophosphorus ester based flame retardant heat endurance during preparation and use is low, volatility is big, easily migration
Thus affecting material property.9,10- dihydro-9-oxy -10- phospho hetero phenanthrene -10- oxides are that a kind of flame retarding efficiency is high, environmental friendliness
The phosphorous reactive flame retardant of type, itself has anti-flammability.Due to containing active hydrogen in its structure, can carry out with multiple compounds
React so warp prepares fire retardant frequently as intermediate, but, find the poor-performing of resistance to molten drop of sample in use.
Multielement synergistic fire retardant is considered as preferable fire retardant.Document report(Polym. Degr. Stab.,
2009, 94:1693-1699;Ind. Eng. Chem. Res., 2011, 50: 1881-1892;Polym. Degr.
Stab., 2011, 96: 1720-1724)Phosphorus-nitrogen containing flame retardant, with phosphorus, nitrogen as active component, can play during fire-retardant
Significantly phosphorus nitrogen synergy, forms heat-insulated, oxygen barrier and the foamed char full of inert gas, and producing ratio individually contains phosphorus or nitrogen
The more excellent flame retardant effect of fire retardant.
Silicon-containing compound can make the high silica of layer of charcoal surface distributed heat endurance, thus preventing under high temperature after decomposing
The decomposition further of layer of charcoal, has certain anti-flammability by this silicon-containing compound.In addition silicon-containing compound has excellent heat surely
Qualitative, surface energy is low, and oxidation resistance is strong, and moisture-proof is good, the features such as chain pliability is high.Document report(J. Polym.
Sci. B Polym. Phys., 2010, 48: 693-705; Polym. Degrad. Stab., 2011, 96: 1508-
1515;J. Polym. Sci. B Polym. Phys., 2007, 45: 1542-1551)Phosphorus silicon-series five-retardant makes material
Fire resistance improves, and compared with fire retardant phosphorous merely, phosphorus silicon-series five-retardant generally will not reduce modified resin
Heat endurance, material heat release rate in thermal decomposition process substantially slows down, and the carbon left after decomposition also accordingly increases.
In sum, halogen flame environmental pollution is larger, and business-like environment-friendly type phosphorus flame retardant has anti-melting
Dripping property and hydrolytic resistance are poor, and the defect that the heat endurance of addition ambassador's resin declines.When phosphorus is common with silicon or nitrogen
Cooperative effect can be produced during same-action, not only make fire retardant have excellent fire resistance, flame-retardant system can also be improved
Mechanical performance and heat endurance.But in document, the report of synergistic flame retardant is focused mostly on and phosphorus nitrogen and phosphorus silicon type fire retardant, and
Structure and complicated process of preparation, have such problems as bad with resin compatible simultaneously.Do not see at present with regard to containing phosphorus,
Nitrogen, the report of the macromolecular fire retardant of three kinds of elements of silicon.
Content of the invention
The present invention provides a class to contain phosphorus, nitrogen, the macromolecular fire retardant of three kinds of elements of silicon and preparation method thereof, and such is fire-retardant
Agent preparation is simple, three kinds of element cooperative flame retardants, and the flame retardant resin systems for obtaining high flame retardant and function admirable provide new way
And new method.
Specifically, the present invention includes:
One class contains the macromolecular fire retardant of phosphorus, nitrogen, three kinds of elements of silicon it is characterised in that structural formula(Ⅰ)As follows:
(Ⅰ)
Wherein, R1, R2, R3, R4Identical or different, and independently selected from C1-C12Alkyl, N, O, S hetero atom replace
C1-C12Alkyl, C6-C22Aryl, C1-C12Alkoxyl, or a combination thereof;
R1, R2, R3, R4Identical or different, it preferably is selected from C1-C3Alkyl and C6-C12Aryl;
M is selected from C1-C12Alkyl, phenyl, hydroxyl substituted-phenyl, C1-C12Alkyl-substituted phenyl, naphthyl, C11-C22's
Alkyl-substituted naphthaline base, hydroxyl substituted naphthyl;
M preferably is selected from hydroxyl substituted-phenyl and hydroxyl substituted naphthyl;
n=0-50.
Containing phosphorus, nitrogen, the macromolecular fire retardant of three kinds of elements of silicon method it is characterised in that make comprise following substance A
Reacted with the mixture of aldehyde material:
Substance A is formula(Ⅱ)Organosilicon polymer:
(Ⅱ)
Aldehyde material for formula is(Ⅲ)Compound:
(Ⅲ)
Wherein R1, R2, R3, R4Identical or different, and independently selected from C1-C12Alkyl, N, O, S hetero atom replace C1-
C12Alkyl, C6-C22Aryl, C1-C12Alkoxyl, or a combination thereof;
M is selected from C1-C12Alkyl, phenyl, hydroxyl substituted-phenyl, C1-C12Alkyl-substituted phenyl, naphthyl, C1-C12Alkane
Base substituted naphthyl, hydroxyl substituted naphthyl;
n=0-50.
Preparation containing phosphorus, nitrogen, the macromolecular fire retardant of three kinds of elements of silicon method, its reaction comprises following synthesis step:
By organosilicon polymer(Structure is as shown in formula II)With solvent be added to anti-with agitating device and temperature regulating device
Answer in device, aldehyde material(Structure is as shown in formula III)According to aldehyde radical and amino mol ratio 1:1 amount is added in reactor, temperature
Control and react 1 ~ 10 hour under the conditions of 0 ~ 50 DEG C, obtain imine intermediate after the completion of reaction, be directly used in the next step;
9,10- dihydro -9- oxa- -10- phospho hetero phenanthrene -10- oxide is pressed the mol ratio 1 of P-H and amino:1 addition
To in the above-mentioned reaction system containing imine intermediate, temperature control is reacted 1 ~ 20 hour under the conditions of 0 ~ 50 DEG C, and reaction terminates
Afterwards, cool down, remove solvent, through recrystallization or column chromatography purification, obtain solid.
Described solvent is that the combination of one or more of dichloromethane, chloroform, methyl alcohol, ethanol, ethylene glycol, dioxane is molten
Agent.
A class according to claim 1 contain phosphorus, nitrogen, three kinds of elements of silicon macromolecular fire retardant it is characterised in that:
Such compound can be used as the halogen-free flameproof of the engineering plastics such as epoxy resin, polyurethane, ABS, nylon.
The effect of the present invention:Contain phosphorus, silicon, three kinds of nitrogen fire-retardant in the BACN molecular structure of designed synthesis simultaneously
Element, fire resistance significantly improves;Due to introducing poly- silica chain in molecular structure, this based flame retardant is made to be added in resin system
There is good compatibility;The resin adding this based flame retardant has preferable heat endurance;Containing phosphorus silicon nitrogen of the present invention fire-retardant
Agent is not halogen-containing, is conducive to environmental protection;The fire-retardant FRW process is simple of containing phosphorus silicon nitrogen of the present invention, is suitable for large-scale production.
Synthetic example
The synthesis of embodiment 1 fire retardant DPP-Si-1
(Ⅳ)
The building-up process of fire retardant DPP-Si-1 is shown in above formula(Ⅳ).
Equipped with condenser pipe, in 100 mL there-necked flasks of thermometer and magnetic agitation, add amido silicon oil(SiONH2,
20.0 g, 0.023 mol), parahydroxyben-zaldehyde(5.1 g, 0.041 mol)With 30 mL dichloromethane, under nitrogen protective condition
Reaction room temperature reaction, after 3 hours, is dividedly in some parts DOPO(8.9 g, 0.041 mol), continue reaction, by a plate(Solvent is
Chloroform/methanol=4:1)Detection reaction is carried out, and reacts 6 hours about, and DOPO reaction is complete, after revolving removes solvent, by silica gel
Post carries out column chromatography purification(Eluent:Chloroform/methanol=10:1), after removing solvent, obtain yellow blocks of solid DPP-Si-1
24.8g(Yield:79.5 % ).IR(KBr)νmax(cm−1) :3305 (-OH); 2954~2846 (CH3and CH2);
1606,1523,1452 (Ar ring); 1187 (P=O); 1267(Si-CH3); 1040~1092 (Si-O-Si); 921
(P-O-C).1H-NMR(CDCl3, 400MHz) δppm: -0.14~0.21(-Si-CH3), 0.25~0.35(m, Si-CH2),
1.25~1.39(m, Si-CH2-CH 2 -), 2.21~2.58(m, -NH-+-NH-CH 2 -), 4.01~4.22(d, -P-CH-),
6.57~8.06(m, Ar-H), 9.83(s, -OH).31P-NMR (CDCl3, 400MHz)δppm: 20~25.
The synthesis of embodiment 2 fire retardant DPP-Si-2
(Ⅴ)
The building-up process of fire retardant DPP-Si-2 is shown in above formula(Ⅴ).
By amido silicon oil(SiONH2)(20.0g, 0.023mol), benzaldehyde(4.3g, 0.041mol)With 30mL dichloromethane
Alkane adds equipped with condenser pipe, in the 100mL there-necked flask of thermometer and magnetic agitation, reacts room temperature reaction under nitrogen protective condition
After 3 hours, add DOPO(8.9g, 0.041mol), by a plate(Solvent:Chloroform/methanol=5:1)Detection reaction is carried out, about
After 8 hours, completely, revolving removes solvent, carries out column chromatography purification by silicagel column for DOPO reaction(Eluent:Chloroform/methanol=
12:1), after removing solvent, obtain faint yellow dope DPP-Si-2 23.8g(Yield:77.9 % ).IR(KBr)νmax(cm−1) :3071(Ar-H); 2964~2894 (CH3and CH2); 1599,1460 (Ar ring); 1193 (P=O);
1257(Si-CH3); 1043~1097 (Si-O-Si); 921 (P-O-C).1H- NMR (CDCl3, 400MHz): δppm= -
0.04~0.30 (-Si-CH3), 0.39~0.49 (Si-CH2), 1.13~1.59 (Si-CH2-CH 2 -), 2.14~2.84
(m, -NH-+-NH-CH 2 -), 4.10~4.32 (-P-CH-), 6.49~8.12 (Ar-H).31P-NMR (CDCl3,
400MHz)δppm: 16~24.
Application Example
The test bars being used for anti-flammability in the present invention are in high-pressure sodium lamp(λmax= 365 nm, I = 1 mW∙cm-2)
Carry out preparation under heat cure again after irradiating the lower initiation photocuring by light trigger.Light trigger be cyclopentadienyl group-iron-
(N- ethyl) carbazole hexafluorophosphate(In-Fe, is shown in formula(Ⅵ)), epoxy monomer used is a kind of alicyclic ring type of bifunctionality
Epoxide(ERL4221, is shown in formula(Ⅶ)).
(Ⅵ)
(Ⅶ)
Oxygen index (OI)(LOI)Mensure use instrument be JF-3 type oxygen index instrument, content according to GB/T 2406-1993
Tested, the size of batten is 100 mm × 6.5 mm × 3 mm;
Before sample preparation first by epoxy monomer ERL4221 in 25 mmHg, vacuum distillation 3 hours under the conditions of 120 DEG C, remove resin
Middle remaining moisture.
Embodiment 1
The fire retardant DPP-Si-1 of 5wt%, 10wt% and 15wt% is separately added in ERL4221, makes three groups of samples, plus
After heat is thoroughly mixed uniformly to 110 DEG C, it is cooled to 80 DEG C, maintains this temperature to stir under the conditions of lucifuge whole to light trigger
Dissolving.The liquid mixture of gained is poured into from molding jig, after high voltage mercury lamp radiation 10min, takes out, in an oven
Under the conditions of 120 DEG C, heating 30min carries out solidify afterwards process, solidfied material is obtained required batten size after polishing, respectively obtains
Sample EPDS1-5, EPDS1-10 and EPDS1-15 after the solidification of three different flame retardant additions.
Sample after obtained solidification is measured heat decomposition temperature and remaining carbon by thermal analyzer, data is listed in table 1.
Sample after obtained solidification is carried out oxygen index (OI) test, data is listed in table 2.
As can be seen from Table 1 and Table 2, for sample EPDS1-15, system oxygen index (OI) reaches 27.2, corresponding weightlessness
The heat decomposition temperature of 10wt% is 368 DEG C.Show the good flame retardant effect that prepared fire retardant plays to system, simultaneously solid
Change resin and there is very high heat decomposition temperature.
Embodiment 2
The fire retardant DPP-Si-2 of 5wt%, 10wt% and 15wt% is separately added in ERL4221, makes three groups of samples, plus
After heat is thoroughly mixed uniformly to 110 DEG C, it is cooled to 80 DEG C, maintains this temperature to stir under the conditions of lucifuge whole to light trigger
Dissolving.The liquid mixture of gained is poured into from molding jig, after high voltage mercury lamp radiation 10min, takes out, in an oven
Under the conditions of 120 DEG C, heating 30min carries out solidify afterwards process, solidfied material is obtained required batten size after polishing, respectively obtains
Sample EPDS2-5, EPDS2-10 and EPDS2-15 after the solidification of three different flame retardant additions.
Sample after obtained solidification is measured heat decomposition temperature and remaining carbon by thermal analyzer, data is listed in table 1.
Sample after obtained solidification is carried out oxygen index (OI) test, data is listed in table 3.
As can be seen that for sample EPDS2-15, system oxygen index (OI) reaches 24.2, corresponding weightlessness from table 1 and table 3
The heat decomposition temperature of 10wt% is 358 DEG C.
Claims (5)
1. a class contains the macromolecular fire retardant of phosphorus, nitrogen, three kinds of elements of silicon it is characterised in that structural formula (I) is as follows:
Wherein, R1, R2, R3, R4Identical or different, and independently selected from C1-C12Alkyl, N, O, S hetero atom replace C1-C12's
Alkyl, C6-C22Aryl, C1-C12Alkoxyl, or a combination thereof;
M is selected from C1-C12Alkyl, phenyl, hydroxyl substituted-phenyl, C1-C12Alkyl-substituted phenyl, naphthyl, C1-C12Alkyl take
For naphthyl, hydroxyl substituted naphthyl;
N=0-50.
2. according to claim 1 containing phosphorus, nitrogen, three kinds of elements of silicon macromolecular fire retardant it is characterised in that:By such
Compound is used for the halogen-free flameproof of engineering plastics.
3. according to claim 1 containing phosphorus, nitrogen, three kinds of elements of silicon macromolecular fire retardant it is characterised in that:By such
Compound is used for epoxy resin, polyurethane, ABS, the halogen-free flameproof of nylon.
4. a kind of prepare claim 1 containing phosphorus, nitrogen, the macromolecular fire retardant of three kinds of elements of silicon method, its reaction comprises
Following synthesis step:
Organosilicon polymer (structure is as shown in formula II) and solvent are added to the reactor with agitating device and temperature regulating device
In, aldehyde material (structure is as shown in formula III) is according to aldehyde radical and amino mol ratio 1:1 amount is added in reactor, temperature control
React 1~10 hour under the conditions of 0~50 DEG C, obtain imine intermediate after the completion of reaction, be directly used in the next step;
Wherein R1, R2, R3, R4Definition as claimed in claim 1;
The definition of n is as claimed in claim 1;
M-CHO
(Ⅲ)
The wherein definition of M is as claimed in claim 1;
Miscellaneous for 9,10- dihydro-9-oxy -10- phospho hetero phenanthrene -10- oxide is pressed the mol ratio 1 of P-H and amino:1 is added to above-mentioned containing
Have in the reaction system of imine intermediate, temperature control is reacted 1~20 hour under the conditions of 0~50 DEG C, after reaction terminates, cold
But, remove solvent, through recrystallization or column chromatography purification, obtain solid.
5. preparation claim 1 according to claim 4 containing phosphorus, nitrogen, the macromolecular fire retardant of three kinds of elements of silicon
Method is it is characterised in that described solvent is one of dichloromethane, chloroform, methyl alcohol, ethanol, ethylene glycol, dioxane or many
The combination solvent planted.
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