CN106588978A - Phosphate ester fire retardant based on biomass and preparation method thereof - Google Patents
Phosphate ester fire retardant based on biomass and preparation method thereof Download PDFInfo
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- CN106588978A CN106588978A CN201611098304.1A CN201611098304A CN106588978A CN 106588978 A CN106588978 A CN 106588978A CN 201611098304 A CN201611098304 A CN 201611098304A CN 106588978 A CN106588978 A CN 106588978A
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- Prior art keywords
- biomass
- eugenol
- phosphate ester
- preparation
- suspensoid
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 76
- 239000010452 phosphate Substances 0.000 title claims abstract description 76
- 239000002028 Biomass Substances 0.000 title claims abstract description 70
- -1 Phosphate ester Chemical class 0.000 title claims abstract description 61
- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 152
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000005770 Eugenol Substances 0.000 claims abstract description 76
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229960002217 eugenol Drugs 0.000 claims abstract description 76
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 21
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 70
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 69
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 42
- 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 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 239000012044 organic layer Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 8
- 241000628997 Flos Species 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- HDXPALCKZHUKRL-UHFFFAOYSA-N chloromethane phosphoryl trichloride Chemical class ClC.ClP(Cl)(Cl)=O HDXPALCKZHUKRL-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 239000000463 material Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 7
- 239000003245 coal Substances 0.000 abstract description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000003208 petroleum Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 229940050176 methyl chloride Drugs 0.000 abstract 1
- 238000002390 rotary evaporation Methods 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 50
- 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 34
- 239000011734 sodium Substances 0.000 description 34
- 229910052708 sodium Inorganic materials 0.000 description 34
- 239000000243 solution Substances 0.000 description 34
- 235000011121 sodium hydroxide Nutrition 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 18
- 235000002639 sodium chloride Nutrition 0.000 description 17
- 239000011780 sodium chloride Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 11
- 238000013019 agitation Methods 0.000 description 10
- 235000011837 pasties Nutrition 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 244000223014 Syzygium aromaticum Species 0.000 description 2
- 235000016639 Syzygium aromaticum Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000000686 essence Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a phosphate ester fire retardant based on biomass and a preparation method thereof. According to the invention, under alkali metal highly basic effect, eugenol from the biomass forms a eugenol salt suspensoid; a methyl chloride solution of phosphorous oxychloride is dropped in the eugenol salt suspensoid, after a reaction is completed, a solvent is removed through washing and rotary evaporation to obtain the liquid phosphate ester fire retardant based on the biomass under normal temperature. The biomass content in the phosphate ester fire retardant can reach as high as 91.2%, and the phosphate ester fire retardant contains an allyl group, is subjected to copolymerization with a plurality of materials, and can increase the compatibility of the fire retardant and the material, and the obtained flame retardation high-molecular material has excellent flame resistance. The preparation method has the advantages of simple process, short synthesis period, and high yield; the raw materials are recycled and regenerable, are in favor of reducing the consumption of the organophosphate fire retardants on the non renewable petroleum and coal resource, and the method has application prospect.
Description
Technical field
The present invention relates to a kind of fire retardant and preparation method thereof, and in particular to a kind of resistance based on green renewable biomass
Combustion agent and preparation method thereof.
Background technology
Macromolecular material is one of traditional three big materials, and it is applied to the every field of national economy and people's lives.With
People to safety, the highest attention of sustainable development, high molecular fire retardant material becomes the important content of material development.But,
Macromolecular material itself does not have good anti-flammability.
The global fire retardant consumption figure of 2012 is about 1,970,000 tons.Predicted, global retardant requirement amount will be with average annual 5%
Speed increase, it is contemplated that by 2018, global fire retardant consumption figure was up to 2,600,000 tons.The industrially maximum resistance of consumption at present
Combustion agent is aluminium hydroxide, halogenated flame retardant, phosphorus flame retardant.Aluminium hydroxide is main inorganic combustion inhibitor, with its good heat
Stability, nontoxic non-corrosiveness gas are widely used the advantages of releasing, account for the 80% of inorganic combustion inhibitor total amount with
On, but addition is up to 40～60% could meet fire-retardant demand, high filler loading capacity necessarily cause the molding processibility of resin and
Mechanical performance declines.The gas that halogenated flame retardant is generated when burning has severe corrosive, and serious pollution is caused to environment, affects
The mankind's is healthy, has been limited by multiple international organizations and has been used.Phosphorus flame retardant have low toxicity, it is efficient the characteristics of, recognized
To be the strong replacement fire retardant kind of halogenated flame retardant.
Phosphorus in phosphorus flame retardant（Phosphine）The acid esters kind huge market demand.Wherein, triphenyl phosphate and tricresyl phosphate
It is the most frequently used commercialization aromatic phosphoric ester, their preparation relies primarily on the phenol and cresol based on coal and petroleum resources.
As the development prospect of the not very reduction of oil and coal resource storage capacity, coal and oil based flameproofing will also face ultimate challenge.
Therefore in the urgent need to reproducible biological material prepares phosphate ester, but phosphate ester based on biomass and preparation method thereof is still
It is not seen in report.Additionally, traditional phosphate ester is without reactive group, when with flame retarded polymeric material is prepared, exist
The problems such as volatility is big, the compatibility is not good.
Eugenol（Coryophyllic acid）, molecular formula is C10H12O2, it is colourless to weak yellow liquid, have strong
Cloves fragrance, it is water insoluble.It accounts for the composition of Oleum Caryophylli 80%, and Oleum Caryophylli is refined from plant of clove and obtained.Eugenol
It is the relatively low biological material of a kind of reproducible and price.It is mainly used in antibacterial, blood pressure lowering；It is also used for perfume fragrant
In smart and various cosmetic essences and fragrance for detergents formula, it may also be used for the allotment of essence.In recent years, eugenol is in macromolecule
There is preliminary application in synthesis field, but has not been reported as fire retardant is prepared.
The content of the invention
A kind of deficiency that the present invention exists for existing phosphate ester flame retardants, there is provided the green reproducible base of response type
Phosphate flame retardant in biomass and preparation method thereof, can make phosphate ester have the more preferable compatibility, energy with macromolecular material
Effectively improve the flame retarding efficiency of macromolecular material.
To achieve the above object of the invention, the technical solution adopted in the present invention is a kind of organic phosphate flame-retardant based on biomass
The preparation method of agent, comprises the steps：
（1）Under conditions of temperature is for 0.5～4.5 DEG C, by mol, by 300～400 parts of alkali metal highly basic and 180～280 parts
Water mix homogeneously, obtains pastel A；
（2）300～400 parts of eugenol are dissolved in 1500～2600 parts of chloromethanes, eugenol chloromethanes solution is obtained, are stirred
Under the conditions of, in being added drop-wise to pastel A, Flos Caryophylli phenates suspensoid B is obtained；
（3）100 parts of phosphorus oxychloride are dissolved in 800～1600 parts of chloromethanes solution, phosphorus oxychloride chloromethanes solution is obtained,
Temperature is under conditions of 0～30 DEG C, in being slowly dropped to Flos Caryophylli phenates suspensoid B, after completion of dropping in 2～4h, continuation is anti-
Answer 2～4h；Again with alkali metal strong base solution extract and separate organic layer, revolving removes solvent after washing, drying, obtains light yellow liquid
Body, as a kind of phosphate flame retardant based on biomass.
Alkali metal highly basic described in technical solution of the present invention be sodium hydroxide, potassium hydroxide in one kind, or they appoint
Meaning combination.
Described chloromethanes are the one kind in dichloromethane, chloroform, or their combination in any.
Technical solution of the present invention also includes being prepared as described above a kind of phosphate flame retardant based on biomass that method is obtained.
Compared with prior art, the beneficial effect of present invention acquirement is：
1st, unlike the prior art, the phosphate flame retardant based on biomass that the present invention is provided from renewable biomass providing
The eugenol in source is raw material, and biomass content is up to 91.2%.Eugenol is a kind of renewable, low toxicity, relatively low cost
（About 5 dollars of per kilogram）Biological material.And it is coal and petroleum base phenol as a kind of biomass phenol compound
With the potential succedaneum of cresol；It is based on the organic phosphate flame-retardant of biomass even more because eugenol contains reactive allyl group
There is reactivity to provide condition for agent.
2nd, unlike the prior art, allyl functionality is contained based on the phosphate flame retardant of biomass, can be with various materials
Material is copolymerized, compatible so as to what is existed when solving traditional coal and petroleum base phosphate ester as additive flame retardant addition polymer
Property it is not good, the problems such as volatility is big, be conducive to giving full play to for fire retardation, also established base for being further modified for phosphate ester
Plinth.
3rd, a kind of phosphate flame retardant based on biomass that the present invention is provided has an environmental protection, preparation process is simple,
Synthesis cycle is short, and yield is high, and process control is good, it is easy to the characteristics of industrialized production.
Description of the drawings
Fig. 1 is phosphate synthesis reaction equation of the embodiment of the present invention 1 based on biomass.
Fig. 2 is proton nmr spectra of the embodiment of the present invention 1 based on the phosphate ester of biomass.
Fig. 3 is carbon-13 nmr spectra of the embodiment of the present invention 1 based on the phosphate ester of biomass.
Fig. 4 is nuclear magnetic resonance, NMR phosphorus spectrum of the embodiment of the present invention 1 based on the phosphate ester of biomass.
Fig. 5 is high resolution mass spectrum figure of the embodiment of the present invention 1 based on the phosphate ester of biomass.
Fig. 6 is the bismaleimide that the flame-retardant bismaleimide resin that comparative example of the present invention 1 is provided is provided with comparative example 2
HRR-the time graph of polyimide resin（Taper calorimetric test result）Comparison diagram.
Specific embodiment
With reference to the accompanying drawings and examples technical solution of the present invention will be further described.
Embodiment 1
Referring to accompanying drawing 1, it is phosphate synthesis reaction equation of the present invention based on biomass, and as shown in Figure 1, the reaction is phosphoric acid
Esterification；In the present embodiment, specific synthetic method is：Under the conditions of temperature is for 1 ± 0.5 DEG C, by 36.0g sodium hydroxide
Mix with 10mL water, obtain pastel A；Under stirring condition, the Deca eugenol in pastel A（147.8g）Dichloromethane
（300mL）Solution, is obtained eugenol sodium suspensoid B；Then, under conditions of temperature is for 0 DEG C, in eugenol sodium suspensoid B
It is slowly added dropwise phosphorus oxychloride（46.0g）Dichloromethane（200mL）Solution, 2h completion of dropping continues to react 2h；To in reaction bulb
The sodium hydrate aqueous solution of 120g 20% is added, with the Sodium Chloride for removing unreacted eugenol and generate.Extract and separate goes out to have
Machine layer, with saturated common salt neutrality, anhydrous sodium sulfate drying are washed to.Revolving removes solvent, obtains weak yellow liquid, is as based on
The phosphate ester of biomass.Its proton nmr spectra, carbon spectrum, phosphorus spectrum and high resolution mass spectrum figure are respectively referring to accompanying drawing 2,3,4 and 5.
Referring to accompanying drawing 2, it is the proton nmr spectra of the phosphate ester based on biomass manufactured in the present embodiment；5.92ppm
（Hf）And 5.03-5.10ppm（Hg, Hh）Place represents the H, 3.33ppm being based in the phosphate ester of biomass in allyl double bonds
（He）Place represents the H on methylene adjacent with double bond on pi-allyl, 3.74ppm（Hd）H on place's representation methoxy,
7.30ppm（Ha）6.73ppm（Hc）And 6.69ppm（Hb）Place represents the H on phenyl ring.
Referring to accompanying drawing 3, it is the carbon-13 nmr spectra of the phosphate ester based on biomass manufactured in the present embodiment,
The peak of 138.62ppm and 116.19ppm represents respectively the C on the phosphate ester pi-allyl based on biomass9And C10, 40.15ppm's
Peak represents the C on methylene adjacent with double bond on pi-allyl8, the C on the peak representation methoxy of 56.14ppm7, C1-C6Represent
C atoms on phenyl ring.
Referring to accompanying drawing 4, it is the nuclear magnetic resonance, NMR phosphorus spectrum of the phosphate ester based on biomass manufactured in the present embodiment ,-
15.83ppm occurs in that a sharp peak, shows there was only a kind of phosphorus atoms in molecular structure, is consistent with theory.
Referring to accompanying drawing 5, it is the high resolution mass spectrum figure of the phosphate ester based on biomass manufactured in the present embodiment, based on biology
The theoretical molecular [M] of the phosphate ester of matter is 536.1964, theoretical value [M+H+] it is 537.2037, experiment value is 537.2063,
Theoretical value [M+Na+] it is 503.1313, experiment value is 503.1306, and experiment value is consistent with theoretical value.
Comprehensive the figures above understands that product manufactured in the present embodiment is a kind of response type phosphate ester with pi-allyl.
Comparative example 1, the preparation of bimaleimide resin：At 130 DEG C, by 50.0g N, N ' -4,4 '-diphenyl-methane
BMI（BDM）With 37.0g 2,2 '-diallyl bisphenol（DBA）Mixing, stirs pre-polymerization 30min at 145 DEG C,
Obtain the transparent supernatant liquid of brown color.Liquid is poured in mould, the evacuation 30min at 150 DEG C, then with 150 DEG C/2h+180
DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h techniques are solidified respectively and post processing.Room temperature is cooled to, that is, obtains double
Maleimide resin.
Comparative example 2, the preparation based on the phosphate flame retardant modified bismaleimide resin of biomass：It is in temperature
Under conditions of 130 DEG C, by 50.0g N, N ' -4,4 '-diphenyl methane dimaleimide（BDM）, the allyls of 9.7g 2,2 '-two
Base bisphenol-A（DBA）Phosphate ester based on biomass manufactured in the present embodiment with 31.7g mixes, under conditions of temperature is for 145 DEG C
Stirring pre-polymerization 30min, obtains the transparent supernatant liquid of brown color.Liquid is poured in mould, the evacuation under 150 DEG C of temperature conditionss
30min, then solidification and rear place are carried out respectively with 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h techniques
Reason.Room temperature is cooled to, that is, is obtained based on the phosphate flame retardant modified bismaleimide resin of biomass, its phosphorus content is
2%。
Referring to accompanying drawing 6, it is bimaleimide resin prepared by comparative example 1 and prepared by comparative example 2 based on biomass
Phosphate flame retardant modified bismaleimide resin HRR-time graph comparison diagram（Taper calorimetric test knot
Really）.Therefrom visible, the maximum HRR of bimaleimide resin prepared by comparative example 1 is 247.3kW/m2；And compare
The maximum HRR of the phosphate flame retardant modified bismaleimide resin based on biomass prepared by example 2 is
91.3kW/m2, the maximum HRR for comparing the resin of comparative example 1 reduces 63.1%, show present invention preparation based on biology
The phosphate flame retardant of matter has significant flame retardant effect.
Embodiment 2
At 2 ± 0.5 DEG C, 42.0g sodium hydroxide is mixed with 13mL water, obtain pastel A, under agitation, in pasty state
Deca eugenol in thing A（172.4g）Dichloromethane（400mL）Solution, is obtained eugenol sodium suspensoid B.Then, at 20 DEG C
Under, it is slowly added dropwise phosphorus oxychloride in eugenol sodium suspensoid B（46.0g）Dichloromethane（250mL）Solution, 3h is dripped
Finish, continue to react 3h.Reaction terminates the sodium hydrate aqueous solution that 200g 10% is added in backward reaction bulb, unreacted to remove
Eugenol and the Sodium Chloride for generating.Extract and separate goes out organic layer, and with saturated common salt neutrality, anhydrous sodium sulfate drying are washed to.Will
Solvent revolving is removed, and obtains weak yellow liquid, the i.e. phosphate ester based on biomass.
Embodiment 3
At 3 ± 0.5 DEG C, 48.0g sodium hydroxide is mixed with 15mL water, obtain pastel A, under agitation, in pasty state
Thing A and the Sodium Chloride for generating.Extract and separate goes out organic layer, and with saturated common salt neutrality, anhydrous sodium sulfate drying are washed to.Revolving is removed
Solvent is removed, weak yellow liquid, the as phosphate ester based on biomass is obtained.Its proton nmr spectra, carbon spectrum, phosphorus spectrum and high score
Distinguish mass spectrum respectively referring to accompanying drawing 2,3,4 and 5.
Referring to accompanying drawing 2, it is the proton nmr spectra of the phosphate ester based on biomass manufactured in the present embodiment；5.92ppm
（Hf）And 5.03-5.10ppm（Hg, Hh）Place represents the H, 3.33ppm being based in the phosphate ester of biomass in allyl double bonds
（He）Place represents the H on methylene adjacent with double bond on pi-allyl, 3.74ppm（Hd）H on place's representation methoxy,
7.30ppm（Ha）6.73ppm（Hc）And 6.69ppm（Hb）Place represents the H on phenyl ring.
Referring to accompanying drawing 3, it is the carbon-13 nmr spectra of the phosphate ester based on biomass manufactured in the present embodiment,
The peak of 138.62ppm and 116.19ppm represents respectively the C on the phosphate ester pi-allyl based on biomass9And C10, 40.15ppm's
Peak represents the C on methylene adjacent with double bond on pi-allyl8, the C on the peak representation methoxy of 56.14ppm7, C1-C6Represent
C atoms on phenyl ring.
Referring to accompanying drawing 4, it is the nuclear magnetic resonance, NMR phosphorus spectrum of the phosphate ester based on biomass manufactured in the present embodiment ,-
15.83ppm occurs in that a sharp peak, shows there was only a kind of phosphorus atoms in molecular structure, is consistent with theory.
Referring to accompanying drawing 5, it is the high resolution mass spectrum figure of the phosphate ester based on biomass manufactured in the present embodiment, based on biology
The theoretical molecular [M] of the phosphate ester of matter is 536.1964, theoretical value [M+H+] it is 537.2037, experiment value is 537.2063,
Theoretical value [M+Na+] it is 503.1313, experiment value is 503.1306, and experiment value is consistent with theoretical value.
Comprehensive the figures above understands that product manufactured in the present embodiment is a kind of response type phosphate ester with pi-allyl.
Comparative example 1, the preparation of bimaleimide resin：At 130 DEG C, by 50.0g N, N ' -4,4 '-diphenyl-methane
BMI（BDM）With 37.0g 2,2 '-diallyl bisphenol（DBA）Mixing, stirs pre-polymerization 30min at 145 DEG C,
Obtain the transparent supernatant liquid of brown color.Liquid is poured in mould, the evacuation 30min at 150 DEG C, then with 150 DEG C/2h+180
DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h techniques are solidified respectively and post processing.Room temperature is cooled to, that is, obtains double
Maleimide resin.
Comparative example 2, the preparation based on the phosphate flame retardant modified bismaleimide resin of biomass：It is in temperature
Under conditions of 130 DEG C, by 50.0g N, N ' -4,4 '-diphenyl methane dimaleimide（BDM）, the allyls of 9.7g 2,2 '-two
Base bisphenol-A（DBA）Phosphate ester based on biomass manufactured in the present embodiment with 31.7g mixes, under conditions of temperature is for 145 DEG C
Stirring pre-polymerization 30min, obtains the transparent supernatant liquid of brown color.Liquid is poured in mould, the evacuation under 150 DEG C of temperature conditionss
30min, then solidification and rear place are carried out respectively with 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h techniques
Reason.Room temperature is cooled to, that is, is obtained based on the phosphate flame retardant modified bismaleimide resin of biomass, its phosphorus content is
2%。
Referring to accompanying drawing 6, it is bimaleimide resin prepared by comparative example 1 and prepared by comparative example 2 based on biomass
Phosphate flame retardant modified bismaleimide resin HRR-time graph comparison diagram（Taper calorimetric test knot
Really）.Therefrom visible, the maximum HRR of bimaleimide resin prepared by comparative example 1 is 247.3kW/m2；And compare
The maximum HRR of the phosphate flame retardant modified bismaleimide resin based on biomass prepared by example 2 is
91.3kW/m2, the maximum HRR for comparing the resin of comparative example 1 reduces 63.1%, show present invention preparation based on biology
The phosphate flame retardant of matter has significant flame retardant effect.
Embodiment 2
At 2 ± 0.5 DEG C, 42.0g sodium hydroxide is mixed with 13mL water, obtain pastel A, under agitation, in pasty state
Deca eugenol in thing A（172.4g）Dichloromethane（400mL）Solution, is obtained eugenol sodium suspensoid B.Then, at 20 DEG C
Under, it is slowly added dropwise phosphorus oxychloride in eugenol sodium suspensoid B（46.0g）Dichloromethane（250mL）Solution, 3h is dripped
Finish, continue to react 3h.Reaction terminates the sodium hydrate aqueous solution that 200g 10% is added in backward reaction bulb, unreacted to remove
Eugenol and the Sodium Chloride for generating.Extract and separate goes out organic layer, and with saturated common salt neutrality, anhydrous sodium sulfate drying are washed to.Will
Solvent revolving is removed, and obtains weak yellow liquid, the i.e. phosphate ester based on biomass.
Embodiment 3
At 3 ± 0.5 DEG C, 48.0g sodium hydroxide is mixed with 15mL water, obtain pastel A, under agitation, in pasty state
Phosphorus oxychloride is slowly added dropwise in thing A（46.0g）Chloroform（250mL）Solution, 3h completion of dropping continues to react 3h.Reaction
Terminate the sodium hydrate aqueous solution that 200g 10% is added in backward reaction bulb, with the chlorination for removing unreacted eugenol and generate
Sodium.Extract and separate goes out organic layer, and with saturated common salt neutrality, anhydrous sodium sulfate drying are washed to.Solvent is rotated, obtains faint yellow
Liquid, the i.e. phosphate ester based on biomass.
Embodiment 11
At 3 ± 0.5 DEG C, 48.0g sodium hydroxide is mixed with 15mL water, obtain pastel A, under agitation, in pasty state
Deca eugenol in thing A（197.0g）Chloroform（500mL）Solution, is obtained eugenol sodium suspensoid B.Then, at 30 DEG C
Under, it is slowly added dropwise phosphorus oxychloride in eugenol sodium suspensoid B（46.0g）Chloroform（300mL）Solution, 4h is dripped
Finish, continue to react 4h.Reaction terminates the sodium hydrate aqueous solution that 300g 5% is added in backward reaction bulb, unreacted to remove
Eugenol and the Sodium Chloride for generating.Extract and separate goes out organic layer, and with saturated common salt neutrality, anhydrous sodium sulfate drying are washed to.Will
Solvent is rotated, and obtains weak yellow liquid, the i.e. phosphate ester based on biomass.
Embodiment 12
At 4 ± 0.5 DEG C, 50.4g potassium hydroxide is mixed with 10mL water, obtain pastel A, under agitation, in pasty state
Deca eugenol in thing A（147.8g）Chloroform（300mL）Solution, is obtained eugenol sodium suspensoid B.Then, at 0 DEG C
Under, it is slowly added dropwise phosphorus oxychloride in eugenol sodium suspensoid B（46.0g）Chloroform（200mL）Solution, 2h is dripped
Finish, continue to react 2h.Reaction terminates the potassium hydroxide aqueous solution that 168g 20% is added in backward reaction bulb, unreacted to remove
Eugenol and the Sodium Chloride for generating.Extract and separate goes out organic layer, and with saturated common salt neutrality, anhydrous sodium sulfate drying are washed to.Will
Solvent is rotated, and obtains weak yellow liquid, the i.e. phosphate ester based on biomass.
Embodiment 13
At 1 ± 0.5 DEG C, 58.8g potassium hydroxide is mixed with 13mL water, obtain pastel A, under agitation, in pasty state
Deca eugenol in thing A（172.4g）Chloroform（400mL）Solution, is obtained eugenol sodium suspensoid B.Then, at 20 DEG C
Under, it is slowly added dropwise phosphorus oxychloride in eugenol sodium suspensoid B（46.0g）Chloroform（250mL）Solution, 3h is dripped
Finish, continue to react 3h.Reaction terminates the potassium hydroxide aqueous solution that 336g 10% is added in backward reaction bulb, unreacted to remove
Eugenol and the Sodium Chloride for generating.Extract and separate goes out organic layer, and with saturated common salt neutrality, anhydrous sodium sulfate drying are washed to.Will
Solvent is rotated, and obtains weak yellow liquid, the i.e. phosphate ester based on biomass.
Embodiment 14
At 2 ± 0.5 DEG C, 67.2g potassium hydroxide is mixed with 15mL water, obtain pastel A, under agitation, in pasty state
Deca eugenol in thing A（197.0g）Chloroform（500mL）Solution, is obtained eugenol sodium suspensoid B.Then, at 30 DEG C
Under, it is slowly added dropwise phosphorus oxychloride in eugenol sodium suspensoid B（46.0g）Chloroform（300mL）Solution, 4h is dripped
Finish, continue to react 4h.Reaction terminates the potassium hydroxide aqueous solution that 504g 5% is added in backward reaction bulb, unreacted to remove
Eugenol and the Sodium Chloride for generating.Extract and separate goes out organic layer, and with saturated common salt neutrality, anhydrous sodium sulfate drying are washed to.Will
Solvent is rotated, and obtains weak yellow liquid, the i.e. phosphate ester based on biomass.
Embodiment 15
At 3 ± 0.5 DEG C, 18g sodium hydroxide and 25.2g potassium hydroxide are mixed with 10mL water, obtain pastel A, in stirring
Under the conditions of, the Deca eugenol in pastel A（147.8g）Dichloromethane（300mL）Solution, is obtained eugenol sodium suspensoid
B.Then, at 0 DEG C, in eugenol sodium suspensoid B phosphorus oxychloride is slowly added dropwise（46.0g）Dichloromethane（200mL）It is molten
Liquid, 2h completion of dropping continues to react 2h.Reaction terminates the sodium hydrate aqueous solution and 84g that 60g 10% is added in backward reaction bulb
10% potassium hydroxide aqueous solution, with the Sodium Chloride for removing unreacted eugenol and generate.Extract and separate goes out organic layer, uses full
Neutrality, anhydrous sodium sulfate drying are washed to Sal.Solvent is rotated, weak yellow liquid, the i.e. phosphoric acid based on biomass is obtained
Ester.
Embodiment 16
At 4 ± 0.5 DEG C, 24g sodium hydroxide and 33.6g potassium hydroxide are mixed with 15mL water, obtain pastel A, in stirring
Under the conditions of, the Deca eugenol in pastel A（197g）Dichloromethane（300mL）Solution, is obtained eugenol sodium suspensoid B.
Then, at 30 DEG C, in eugenol sodium suspensoid B phosphorus oxychloride is slowly added dropwise（46.0g）Dichloromethane（300mL）It is molten
Liquid, 4h completion of dropping continues to react 4h.Reaction terminate the sodium hydrate aqueous solution that 180g 10% is added in backward reaction bulb and
The potassium hydroxide aqueous solution of 252g 10%, with the Sodium Chloride for removing unreacted eugenol and generate.Extract and separate goes out organic layer,
Neutrality, anhydrous sodium sulfate drying are washed to saturated common salt.Solvent is rotated, weak yellow liquid is obtained, i.e., based on biomass
Phosphate ester.
Embodiment 17
At 1 ± 0.5 DEG C, 21g sodium hydroxide and 29.4g potassium hydroxide are mixed with 13mL water, obtain pastel A, in stirring
Under the conditions of, the Deca eugenol in pastel A（172.4g）Dichloromethane（400mL）Solution, is obtained eugenol sodium suspensoid
B.Then, at 20 DEG C, in eugenol sodium suspensoid B phosphorus oxychloride is slowly added dropwise（46.0g）Dichloromethane（250mL）It is molten
Liquid, 3h completion of dropping continues to react 3h.Reaction terminate the sodium hydrate aqueous solution that 120g 20% is added in backward reaction bulb and
The potassium hydroxide aqueous solution of 168g 20%, with the Sodium Chloride for removing unreacted eugenol and generate.Extract and separate goes out organic layer,
Neutrality, anhydrous sodium sulfate drying are washed to saturated common salt.Solvent is rotated, weak yellow liquid is obtained, i.e., based on biomass
Phosphate ester.
Embodiment 18
At 2 ± 0.5 DEG C, 18g sodium hydroxide and 25.2g potassium hydroxide are mixed with 10mL water, obtain pastel A, in stirring
Under the conditions of, the Deca eugenol in pastel A（147.8g）Chloroform（300mL）Solution, is obtained eugenol sodium suspensoid
B.Then, at 0 DEG C, in eugenol sodium suspensoid B phosphorus oxychloride is slowly added dropwise（46.0g）Chloroform（200mL）It is molten
Liquid, 2h completion of dropping continues to react 2h.Reaction terminates the sodium hydrate aqueous solution and 84g that 60g 10% is added in backward reaction bulb
10% potassium hydroxide aqueous solution, with the Sodium Chloride for removing unreacted eugenol and generate.Extract and separate goes out organic layer, uses full
Neutrality, anhydrous sodium sulfate drying are washed to Sal.Solvent is rotated, weak yellow liquid, the i.e. phosphoric acid based on biomass is obtained
Ester.
Embodiment 19
At 3 ± 0.5 DEG C, 24g sodium hydroxide and 33.6g potassium hydroxide are mixed with 15mL water, obtain pastel A, in stirring
Under the conditions of, the Deca eugenol in pastel A（197g）Chloroform（300mL）Solution, is obtained eugenol sodium suspensoid B.
Then, at 30 DEG C, in eugenol sodium suspensoid B phosphorus oxychloride is slowly added dropwise（46.0g）Chloroform（300mL）It is molten
Liquid, 4h completion of dropping continues to react 4h.Reaction terminate the sodium hydrate aqueous solution that 180g 10% is added in backward reaction bulb and
The potassium hydroxide aqueous solution of 252g 10%, with the Sodium Chloride for removing unreacted eugenol and generate.Extract and separate goes out organic layer,
Neutrality, anhydrous sodium sulfate drying are washed to saturated common salt.Solvent is rotated, weak yellow liquid is obtained, i.e., based on biomass
Phosphate ester.
Embodiment 20
At 4 ± 0.5 DEG C, 21g sodium hydroxide and 29.4g potassium hydroxide are mixed with 13mL water, obtain pastel A, in stirring
Under the conditions of, the Deca eugenol in pastel A（172.4g）Chloroform（400mL）Solution, is obtained eugenol sodium suspensoid
B.Then, at 20 DEG C, in eugenol sodium suspensoid B phosphorus oxychloride is slowly added dropwise（46.0g）Chloroform（250mL）It is molten
Liquid, 3h completion of dropping continues to react 3h.Reaction terminate the sodium hydrate aqueous solution that 120g 20% is added in backward reaction bulb and
The potassium hydroxide aqueous solution of 168g 20%, with the Sodium Chloride for removing unreacted eugenol and generate.Extract and separate goes out organic layer,
Neutrality, anhydrous sodium sulfate drying are washed to saturated common salt.Solvent is rotated, weak yellow liquid is obtained, i.e., based on biomass
Phosphate ester.
Embodiment 21
At 1 ± 0.5 DEG C, 36.0g sodium hydroxide is mixed with 10mL water, obtain pastel A, under agitation, in pasty state
Deca eugenol in thing A（147.8g）Dichloromethane（300mL）Solution, is obtained eugenol sodium suspensoid B.Then, at 0 DEG C
Under, it is slowly added dropwise phosphorus oxychloride in eugenol sodium suspensoid B（46.0g）Dichloromethane（100mL）And chloroform
（100mL）Mixed solution, 2h completion of dropping continues to react 2h.Reaction terminates the hydrogen-oxygen that 120g 20% is added in backward reaction bulb
Change sodium water solution, with the Sodium Chloride for removing unreacted eugenol and generate.Extract and separate goes out organic layer, is washed with saturated common salt
To neutral, anhydrous sodium sulfate drying.Solvent is rotated, weak yellow liquid, the i.e. phosphate ester based on biomass is obtained.
Embodiment 22
At 2 ± 0.5 DEG C, 58.8g potassium hydroxide is mixed with 13mL water, obtain pastel A, under agitation, in pasty state
Deca eugenol in thing A（172.4g）Chloroform（400mL）Solution, is obtained eugenol sodium suspensoid B.Then, at 20 DEG C
Under, it is slowly added dropwise phosphorus oxychloride in eugenol sodium suspensoid B（46.0g）Dichloromethane（125mL）And chloroform
（125mL）Mixed solution, 3h completion of dropping continues to react 3h.Reaction terminates the hydrogen-oxygen that 336g 10% is added in backward reaction bulb
Change aqueous solutions of potassium, with the Sodium Chloride for removing unreacted eugenol and generate.Extract and separate goes out organic layer, is washed with saturated common salt
To neutral, anhydrous sodium sulfate drying.Solvent is rotated, weak yellow liquid, the i.e. phosphate ester based on biomass is obtained.
Embodiment 23
At 3 ± 0.5 DEG C, 24g sodium hydroxide and 33.6g potassium hydroxide are mixed with 15mL water, obtain pastel A, in stirring
Under the conditions of, the Deca eugenol in pastel A（197g）Chloroform（300mL）Solution, is obtained eugenol sodium suspensoid B.
Then, at 30 DEG C, in eugenol sodium suspensoid B phosphorus oxychloride is slowly added dropwise（46.0g）Dichloromethane（150mL）With three
Chloromethanes（150mL）Solution, 4h completion of dropping continues to react 4h.Reaction terminates the hydrogen that 180g 10% is added in backward reaction bulb
The potassium hydroxide aqueous solution of aqueous solution of sodium oxide and 252g 10%, with the Sodium Chloride for removing unreacted eugenol and generate.Extraction
Take and isolate organic layer, with saturated common salt neutrality, anhydrous sodium sulfate drying are washed to.Solvent is rotated, weak yellow liquid is obtained,
Phosphate ester i.e. based on biomass.
Claims (4)
1. a kind of preparation method of the phosphate flame retardant based on biomass, it is characterised in that comprise the steps：
（1）Under conditions of temperature is for 0.5～4.5 DEG C, by mol, by 300～400 parts of alkali metal highly basic and 180～280 parts
Water mix homogeneously, obtains pastel A；
（2）300～400 parts of eugenol are dissolved in 1500～2600 parts of chloromethanes, eugenol chloromethanes solution is obtained, are stirred
Under the conditions of, in being added drop-wise to pastel A, Flos Caryophylli phenates suspensoid B is obtained；
（3）100 parts of phosphorus oxychloride are dissolved in 800～1600 parts of chloromethanes solution, phosphorus oxychloride chloromethanes solution is obtained,
Temperature is under conditions of 0～30 DEG C, in being slowly dropped to Flos Caryophylli phenates suspensoid B, after completion of dropping in 2～4h, continuation is anti-
Answer 2～4h；Again with alkali metal strong base solution extract and separate organic layer, revolving removes solvent after washing, drying, obtains light yellow liquid
Body, as a kind of phosphate flame retardant based on biomass.
2. the preparation method of a kind of phosphate flame retardant based on biomass according to claim 1, its feature in：It is described
Alkali metal highly basic be one kind in sodium hydroxide, potassium hydroxide, or their combination in any.
3. the preparation method of a kind of phosphate flame retardant based on biomass according to claim 1, it is characterised in that：Institute
The chloromethanes stated are the one kind in dichloromethane, chloroform, or their combination in any.
4. a kind of phosphate flame retardant based on biomass for obtaining by claim 1 preparation method.
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| JP7397226B1 (en) * | 2023-02-07 | 2023-12-12 | 四国化成工業株式会社 | Flame retardants and their uses |
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Application publication date: 20170426 |