CN109280218A - A kind of phosphor fluorine containing fire retardant and preparation method thereof and the modified fire retarding epoxide resin of the phosphor fluorine containing fire retardant - Google Patents
A kind of phosphor fluorine containing fire retardant and preparation method thereof and the modified fire retarding epoxide resin of the phosphor fluorine containing fire retardant Download PDFInfo
- Publication number
- CN109280218A CN109280218A CN201810884843.0A CN201810884843A CN109280218A CN 109280218 A CN109280218 A CN 109280218A CN 201810884843 A CN201810884843 A CN 201810884843A CN 109280218 A CN109280218 A CN 109280218A
- Authority
- CN
- China
- Prior art keywords
- fire retardant
- fluorine containing
- phosphor
- phosphor fluorine
- containing fire
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 91
- ZHQXROVTUTVPGO-UHFFFAOYSA-N [F].[P] Chemical compound [F].[P] ZHQXROVTUTVPGO-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 59
- 230000000979 retarding effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 title claims description 58
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 238000007711 solidification Methods 0.000 claims description 19
- 230000008023 solidification Effects 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 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 description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000001723 curing Methods 0.000 claims description 12
- JBGNFLUETJDDBA-UHFFFAOYSA-N n,n-bis(trifluoromethyl)aniline Chemical compound FC(F)(F)N(C(F)(F)F)C1=CC=CC=C1 JBGNFLUETJDDBA-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 10
- 229920002866 paraformaldehyde Polymers 0.000 claims description 10
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical group C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229940106691 bisphenol a Drugs 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 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 abstract description 17
- 239000000463 material Substances 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract 3
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000013006 addition curing Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses the modified fire retarding epoxide resins of a kind of phosphor fluorine containing fire retardant and preparation method thereof and the phosphor fluorine containing fire retardant, wherein the chemical structural formula of phosphor fluorine containing fire retardant is shown below.Contain two kinds of elements of phosphorus fluorine in the phosphor fluorine containing fire retardant, the cooperative flame retardant effect of the two can be improved the flame retardant property of macromolecule matrix, and by condition control can the phosphorus fluorine ratio to fire retardant be adjusted；Due to containing fluorine element in fire retardant, migrate fire retardant can in the base, fire retardant in use can be to resin matrix surface migration, and fire retardant forms concentration gradient distribution in resin matrix, makes it that can improve the flame retardant property and hydrophobic performance of material under few additive.Wherein, R be-H or
Description
Technical field
The invention belongs to organic fire-retardant technical field, in particular to a kind of phosphor fluorine containing fire retardant and preparation method thereof and should
The modified fire retarding epoxide resin of phosphor fluorine containing fire retardant.
Background technique
Due to most high molecular material have the characteristics that it is inflammable, high molecular material it is flame-retardant modified be always
Researchers' problem of concern.In order to improve the flame retardant property of high molecular material, and go out from safe and efficient with environmentally friendly angle
Hair, the fire retardant being widely used now have phosphorus flame retardant, nitrogenated flame retardant, silicon-series five-retardant and inorganic fire retardants etc..
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is a kind of efficient phosphorus flame retardant being widely used, in
State patent application CN201110346692.1 discloses a kind of natural fiber that DOPO is flame-retardant modified enhancing phenolic resin composite wood
Material, improves the flame retardant property of composite material, maintains the mechanical property of material.However, with the development of high molecular weight flame retardant,
Requirement of the people to fire retardant gradually develops from original single flame-retarding characteristic to multi-functional direction, it is desirable to flame-retardant modified
While, assign material new function and characteristic.
Summary of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, provide a kind of phosphor fluorine containing fire retardant and its preparation
The fire retarding epoxide resin that method and the phosphor fluorine containing fire retardant are modified.
The technical solution adopted by the present invention to solve the technical problems first is that:
A kind of phosphor fluorine containing fire retardant, chemical formula are shown below:
Wherein, R be-H or
The technical solution adopted by the present invention to solve the technical problems second is that:
The preparation method of above-mentioned phosphor fluorine containing fire retardant, synthetic route are as follows:
Specific steps include:
Bis- (trifluoromethyl) aniline of 3,5-, DOPO, paraformaldehyde and solvent are added into reaction vessel, at 40~120 DEG C
8~72h of lower back flow reaction, then cooling, which is stood, is precipitated solid to solvent, separates the solid of the precipitation, the as described phosphor fluorine containing resistance
Fire agent.
In one embodiment: the molar ratio of bis- (trifluoromethyl) aniline of the 3,5-, DOPO and paraformaldehyde is 1:1~10:1
~10；The volume ratio of bis- (trifluoromethyl) aniline of the 3,5- and solvent is 1:8~100.
In one embodiment: the solvent be carbon tetrachloride, chloroform, tetrahydrofuran, in N,N-dimethylformamide at least
It is a kind of.
In one embodiment: after the solid for separating the precipitation, placing it in 55~65 DEG C of 22~26h of vacuum drying, i.e.,
Obtain the phosphor fluorine containing fire retardant.
The technical solution adopted by the present invention to solve the technical problems third is that:
A kind of fire retarding epoxide resin that above-mentioned phosphor fluorine containing fire retardant is modified, the fire retarding epoxide resin includes epoxy resin prepolymer
Aggressiveness, the phosphorous nitrogen combustion inhibitor and curing agent, the phosphor fluorine containing fire retardant be the epoxy resin prepolymer 0.1~
50wt%.
In one embodiment: the phosphor fluorine containing fire retardant is introduced into epoxy resin with blending method, prepares corresponding fire-retardant ring
Oxygen resin.
In one embodiment: the epoxy resin prepolymer is E51 bisphenol A type epoxy resin.
In one embodiment: the curing agent is 4,4- diaminodiphenylmethane (DDM).
In one embodiment: the mass ratio of the epoxy resin prepolymer and curing agent is 3~5:1.
The technical solution adopted by the present invention to solve the technical problems fourth is that:
The preparation method of the fire retarding epoxide resin includes: to take the epoxy resin prepolymer, and institute is added at 60~140 DEG C
State phosphor fluorine containing fire retardant, stirring is subsequently added into the curing agent, after being completely dissolved, successively solidifies 3 at 110~130 DEG C to transparent
~5h, 130~150 DEG C of 1~3h of solidification, 170~190 DEG C of 1~3h of solidification, obtain the fire retarding epoxide resin.
The beneficial effects of the present invention are:
(1) contain two kinds of ignition-proof elements of phosphorus and fluorine in phosphor fluorine containing fire retardant, the two has cooperative flame retardant in practical applications
Effect, corresponding fire retarding epoxide resin have the advantages that thermal stability is high, flame retardant property is good；It, can by changing the condition of reaction
To respectively obtain two kinds of different fire retardants of structure, the phosphorus fluorine content of two kinds of fire retardants is different, and two kinds of fire retardants are each advantageous, R
Base is the fire retardant of DOPO and H under identical additive amount, and R base is that the flame retardant effect of DOPO is more preferable, can be according to the need of practical application
It asks and is selected.
(2) contain fluorine element in fire retardant, the material containing fluorine element has the characteristics that surface can be low, therefore can be improved
The hydrophobicity of material；The characteristics of oriented material surface of fluorine element migrates, the migration of fire retardant can be in material as time increases
Expect that surface forms flame resistant protective layer, the flame retardant property of material is further enhanced in use；In addition, ambient enviroment temperature
Degree increases the migration that can also accelerate fire retardant.
(3) economically consider, due to the migration performance of fire retardant, fire retardant forms concentration gradient distribution in resin
(Fig. 1), therefore compared with other fire retardants, the invention can be prepared under low fire retardant additive amount high flame resistance with it is hydrophobic
The resin of performance reduces production cost, in practical applications advantageously.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the concentration gradient distribution situation of phosphor fluorine containing fire retardant in the epoxy.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of phosphor fluorine containing fire retardant in embodiment 1.
Fig. 3 be embodiment 1 in phosphor fluorine containing concentration gradient be distributed fire retarding epoxide resin it is thermally treated before (left side), afterwards (right side) water
Contact angle figure.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment combination attached drawing.
In following embodiments, epoxy resin prepolymer is E51 bisphenol A type epoxy resin.
Embodiment 1
1. preparing phosphor fluorine containing fire retardant:
Be added into reaction flask bis- (trifluoromethyl) aniline of 1mL (6.43mmol) 3,5-, 3.47g (16.07mmol) DOPO,
0.48g (16.07mmol) paraformaldehyde and 30mL chloroform, for 24 hours, then cooling is stood is precipitated back flow reaction to solvent at 50 DEG C
White crystal, is obtained by filtration white solid, and products therefrom is placed in a vacuum drying oven at 60 DEG C and dries for 24 hours to get the R base
For the phosphor fluorine containing fire retardant of-H.
2. preparing fire retarding epoxide resin:
Weigh epoxy resin prepolymer 20g, be warming up to 100 DEG C, be added 10wt% phosphor fluorine containing fire retardant, stirring to transparent,
It is subsequently added into curing agent 4,4- diaminodiphenylmethane (DDM) 5g is subsequently poured into aluminium-making mould, successively exists up to being completely dissolved
120 DEG C of solidification 4h, 140 DEG C of solidification 2h, 180 DEG C of solidification 2h obtain phosphor fluorine containing concentration gradient distribution fire retarding epoxide resin.
It takes obtained flame-retardant epoxy resin to be placed in 120 DEG C of baking ovens to handle for 24 hours, and the water contact angle before and after measurement processing, such as
Shown in Fig. 3, fire retarding epoxide resin water contact angle after heat treatment increases to 90.1 ° from 63.9 °, and the hydrophobicity of resin significantly increases
Greatly.
It is 29.6% according to the oxygen index (OI) that GB/T 2406-2009 measures epoxy resin.
Embodiment 2
1. preparing phosphor fluorine containing fire retardant:
Be added into reaction flask bis- (trifluoromethyl) aniline of 1mL (6.43mmol) 3,5-, 2.92g (13.5mmol) DOPO,
0.41g (13.5mmol) paraformaldehyde and 30mL chloroform, for 24 hours, then cooling is stood is precipitated back flow reaction to solvent at 55 DEG C
White crystal, is obtained by filtration white solid, and products therefrom is placed in a vacuum drying oven at 60 DEG C and dries for 24 hours to get the R base
For the phosphor fluorine containing fire retardant of-H.
2. preparing fire retarding epoxide resin:
Weigh epoxy resin prepolymer 20g, be warming up to 100 DEG C, be added 10wt% phosphor fluorine containing fire retardant, stirring to transparent,
It is subsequently added into curing agent 4,4- diaminodiphenylmethane 5g, until being completely dissolved, is subsequently poured into aluminium-making mould, successively 120
DEG C solidification 4h, 140 DEG C of solidification 2h, 180 DEG C of solidification 2h, obtain phosphor fluorine containing concentration gradient be distributed fire retarding epoxide resin.
It is 29.6% according to the oxygen index (OI) that GB/T 2406-2009 measures epoxy resin.
Embodiment 3
1. preparing phosphor fluorine containing fire retardant:
Be added into reaction flask bis- (trifluoromethyl) aniline of 1mL (6.43mmol) 3,5-, 2.92g (13.5mmol) DOPO,
0.41g (13.5mmol) paraformaldehyde and 30mL N ' dinethylformamide, back flow reaction for 24 hours, then cools down quiet at 60 DEG C
It sets and white crystal is precipitated to solvent, white solid is obtained by filtration, products therefrom, which is placed in a vacuum drying oven at 60 DEG C, to be dried for 24 hours,
The phosphor fluorine containing fire retardant for being-H up to the R base.
2. preparing fire retarding epoxide resin:
Weigh epoxy resin prepolymer 20g, be warming up to 100 DEG C, be added 10wt% phosphor fluorine containing fire retardant, stirring to transparent,
It is subsequently added into curing agent 4,4- diaminodiphenylmethane 5g is subsequently poured into aluminium-making mould, up to being completely dissolved successively at 120 DEG C
Solidify 4h, 140 DEG C of solidification 2h, 180 DEG C of solidification 2h, obtains phosphor fluorine containing concentration gradient distribution fire retarding epoxide resin.
It is 29.6% according to the oxygen index (OI) that GB/T 2406-2009 measures epoxy resin.
Embodiment 4
1. preparing phosphor fluorine containing fire retardant:
Be added into reaction flask bis- (trifluoromethyl) aniline of 1mL (6.43mmol) 3,5-, 3.47g (16.07mmol) DOPO,
0.48g (16.07mmol) paraformaldehyde and 30mL N ' dinethylformamide, back flow reaction for 24 hours, then cools down at 65 DEG C
It stands and white crystal is precipitated to solvent, white solid is obtained by filtration, products therefrom is placed in a vacuum drying oven at 60 DEG C dry
The phosphor fluorine containing fire retardant for being for 24 hours-H to get the R base.
2. preparing fire retarding epoxide resin:
Weigh epoxy resin prepolymer 20g, be warming up to 100 DEG C, be added 10wt% phosphor fluorine containing fire retardant, stirring to transparent,
It is subsequently added into curing agent 4,4- diaminodiphenylmethane 5g is subsequently poured into aluminium-making mould, up to being completely dissolved successively at 120 DEG C
Solidify 4h, 140 DEG C of solidification 2h, 180 DEG C of solidification 2h, obtains phosphor fluorine containing concentration gradient distribution fire retarding epoxide resin.
It is 29.6% according to the oxygen index (OI) that GB/T 2406-2009 measures epoxy resin.
Embodiment 5
1. preparing phosphor fluorine containing fire retardant:
Be added into reaction flask bis- (trifluoromethyl) aniline of 1mL (6.43mmol) 3,5-, 3.47g (16.07mmol) DOPO,
0.48g (16.07mmol) paraformaldehyde and 30mL chloroform, for 24 hours, then cooling is stood is precipitated back flow reaction to solvent at 50 DEG C
White crystal, is obtained by filtration white solid, and products therefrom is placed in a vacuum drying oven at 60 DEG C and dries for 24 hours to get the R base
For the phosphor fluorine containing fire retardant of-H.
2. preparing fire retarding epoxide resin:
Epoxy resin prepolymer 20g is weighed, is warming up to 100 DEG C, is added 5wt% phosphor fluorine containing fire retardant, stirring connects to transparent
Addition curing agent 4,4- diaminodiphenylmethane 5g be subsequently poured into aluminium-making mould until be completely dissolved, it is successively solid at 120 DEG C
Change 4h, 140 DEG C of solidification 2h, 180 DEG C of solidification 2h, obtains phosphor fluorine containing concentration gradient distribution fire retarding epoxide resin.
It is 28.8% according to the oxygen index (OI) that GB/T 2406-2009 measures epoxy resin.
Embodiment 6
1. preparing phosphor fluorine containing fire retardant:
Be added into reaction flask bis- (trifluoromethyl) aniline of 1mL (6.43mmol) 3,5-, 3.47g (16.07mmol) DOPO,
0.48g (16.07mmol) paraformaldehyde and 30mL N ' dinethylformamide, back flow reaction for 24 hours, then cools down at 110 DEG C
It stands and white crystal is precipitated to solvent, white solid is obtained by filtration, products therefrom is placed in a vacuum drying oven at 60 DEG C dry
The phosphor fluorine containing fire retardant for being for 24 hours DOPO to get the R base.
2. preparing fire retarding epoxide resin:
Epoxy resin prepolymer 20g is weighed, is warming up to 100 DEG C, is added 5wt% phosphor fluorine containing fire retardant, stirring connects to transparent
Addition curing agent 4,4- diaminodiphenylmethane 5g be subsequently poured into aluminium-making mould until be completely dissolved, it is successively solid at 120 DEG C
Change 4h, 140 DEG C of solidification 2h, 180 DEG C of solidification 2h, obtains phosphor fluorine containing concentration gradient distribution fire retarding epoxide resin.
It is 28.4% according to the oxygen index (OI) that GB/T 2406-2009 measures epoxy resin.
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to
Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.
Claims (10)
1. a kind of phosphor fluorine containing fire retardant, it is characterised in that: the phosphor fluorine containing fire retardant is shown below:
Wherein, R be-H or
2. a kind of preparation method of phosphor fluorine containing fire retardant described in claim 1, it is characterised in that: 3 are added into reaction vessel,
Bis- (trifluoromethyl) aniline of 5-, DOPO, paraformaldehyde and solvent, 8~72h of back flow reaction at 40~120 DEG C, cooling stand to
Solid is precipitated, separates the solid of the precipitation, the as described phosphor fluorine containing fire retardant.
3. the preparation method of phosphor fluorine containing fire retardant according to claim 2, it is characterised in that: the bis- (fluoroforms of 3,5-
Base) aniline, DOPO and paraformaldehyde molar ratio be 1:1~10:1~10；Bis- (trifluoromethyl) aniline of the 3,5- and solvent
Volume ratio be 1:8~100.
4. the preparation method of phosphor fluorine containing fire retardant according to claim 2, it is characterised in that: the solvent is four chlorinations
At least one of carbon, chloroform, tetrahydrofuran, N,N-dimethylformamide.
5. the preparation method of phosphor fluorine containing fire retardant according to claim 2, it is characterised in that: described to separate consolidating for the precipitation
After body, 55~65 DEG C of 22~26h of vacuum drying are placed it in get the phosphor fluorine containing fire retardant.
6. a kind of fire retarding epoxide resin that phosphor fluorine containing fire retardant described in claim 1 is modified, it is characterised in that: the fire-retardant ring
Oxygen resin includes epoxy resin prepolymer, the phosphorous nitrogen combustion inhibitor and curing agent, and the phosphor fluorine containing fire retardant is the epoxy
0.1~50wt% of resin prepolymer.
7. fire retarding epoxide resin according to claim 6, it is characterised in that: the phosphor fluorine containing fire retardant is drawn with blending method
Enter in epoxy resin, prepares corresponding fire retarding epoxide resin.
8. fire retarding epoxide resin according to claim 6, it is characterised in that: the epoxy resin prepolymer is E51 bisphenol-A
Type epoxy resin；The curing agent is 4,4- diaminodiphenylmethane.
9. fire retarding epoxide resin according to claim 8, it is characterised in that: the epoxy resin prepolymer and curing agent
Mass ratio is 3~5:1.
10. a kind of preparation method of fire retarding epoxide resin as claimed in claim 6, it is characterised in that: take the epoxy resin prepolymer
Aggressiveness, is added the phosphor fluorine containing fire retardant at 60~140 DEG C, and stirring is subsequently added into the curing agent, is completely dissolved to transparent
Afterwards, it successively in 110~130 DEG C of 3~5h of solidification, 130~150 DEG C of 1~3h of solidification, 170~190 DEG C of 1~3h of solidification, obtains described
Fire retarding epoxide resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810884843.0A CN109280218B (en) | 2018-08-06 | 2018-08-06 | Phosphorus and fluorine-containing flame retardant, preparation method thereof and flame-retardant epoxy resin modified by phosphorus and fluorine-containing flame retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810884843.0A CN109280218B (en) | 2018-08-06 | 2018-08-06 | Phosphorus and fluorine-containing flame retardant, preparation method thereof and flame-retardant epoxy resin modified by phosphorus and fluorine-containing flame retardant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109280218A true CN109280218A (en) | 2019-01-29 |
| CN109280218B CN109280218B (en) | 2020-03-06 |
Family
ID=65182936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810884843.0A Active CN109280218B (en) | 2018-08-06 | 2018-08-06 | Phosphorus and fluorine-containing flame retardant, preparation method thereof and flame-retardant epoxy resin modified by phosphorus and fluorine-containing flame retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109280218B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628179A (en) * | 2019-08-30 | 2019-12-31 | 厦门大学 | Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof |
| CN113999342A (en) * | 2021-10-25 | 2022-02-01 | 厦门大学 | Migratable polymer-based functional modifier and preparation method and application thereof |
| CN114752037A (en) * | 2022-04-29 | 2022-07-15 | 青岛富斯林化工科技有限公司 | Preparation method of low-dielectric-resistance flame-retardant epoxy resin |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775445A (en) * | 2012-06-08 | 2012-11-14 | 江苏雅克科技股份有限公司 | Resorcinol-di(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)phosphate (RDD) and preparation method thereof |
| CN102807587A (en) * | 2012-08-15 | 2012-12-05 | 高鼎精细化工(昆山)有限公司 | Phosphorus-fluorine bis-amines compound, preparation method thereof and method for preparing polyimide by using phosphorus-fluorine bis-amines compound |
| CN102875842A (en) * | 2012-09-28 | 2013-01-16 | 沈阳化工大学 | Phosphorus-nitrogen intumescent flame retardant and preparation method thereof |
| CN105732715A (en) * | 2016-01-27 | 2016-07-06 | 厦门大学 | Phosphorus-containing fluorine-containing synergic flame-retardant compound and preparation method thereof |
| CN106832404A (en) * | 2017-02-07 | 2017-06-13 | 东莞市道尔化工有限公司 | Surface migration sex flame retardant of Nitrogen-and Phosphorus-containing and preparation method thereof |
| CN106905370A (en) * | 2017-03-02 | 2017-06-30 | 张家港市山牧新材料技术开发有限公司 | A kind of hydrophobicity DOPO derivative flame retardants and preparation method thereof |
-
2018
- 2018-08-06 CN CN201810884843.0A patent/CN109280218B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775445A (en) * | 2012-06-08 | 2012-11-14 | 江苏雅克科技股份有限公司 | Resorcinol-di(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)phosphate (RDD) and preparation method thereof |
| CN102807587A (en) * | 2012-08-15 | 2012-12-05 | 高鼎精细化工(昆山)有限公司 | Phosphorus-fluorine bis-amines compound, preparation method thereof and method for preparing polyimide by using phosphorus-fluorine bis-amines compound |
| CN102875842A (en) * | 2012-09-28 | 2013-01-16 | 沈阳化工大学 | Phosphorus-nitrogen intumescent flame retardant and preparation method thereof |
| CN105732715A (en) * | 2016-01-27 | 2016-07-06 | 厦门大学 | Phosphorus-containing fluorine-containing synergic flame-retardant compound and preparation method thereof |
| CN106832404A (en) * | 2017-02-07 | 2017-06-13 | 东莞市道尔化工有限公司 | Surface migration sex flame retardant of Nitrogen-and Phosphorus-containing and preparation method thereof |
| CN106905370A (en) * | 2017-03-02 | 2017-06-30 | 张家港市山牧新材料技术开发有限公司 | A kind of hydrophobicity DOPO derivative flame retardants and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628179A (en) * | 2019-08-30 | 2019-12-31 | 厦门大学 | Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof |
| CN110628179B (en) * | 2019-08-30 | 2020-11-17 | 厦门大学 | Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof |
| CN113999342A (en) * | 2021-10-25 | 2022-02-01 | 厦门大学 | Migratable polymer-based functional modifier and preparation method and application thereof |
| CN113999342B (en) * | 2021-10-25 | 2022-08-12 | 厦门大学 | Migratable polymer-based functional modifier and preparation method and application thereof |
| CN114752037A (en) * | 2022-04-29 | 2022-07-15 | 青岛富斯林化工科技有限公司 | Preparation method of low-dielectric-resistance flame-retardant epoxy resin |
| CN114752037B (en) * | 2022-04-29 | 2024-02-09 | 青岛富斯林化工科技有限公司 | Preparation method of low-dielectric flame-retardant epoxy resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109280218B (en) | 2020-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106750239A (en) | A kind of phosphorus-nitrogen containing fluoropolymer fire retardant and preparation method and application | |
| CN109280218A (en) | A kind of phosphor fluorine containing fire retardant and preparation method thereof and the modified fire retarding epoxide resin of the phosphor fluorine containing fire retardant | |
| WO2018095357A1 (en) | Fluorine-containing silicon polyphosphate ester and method for preparation thereof | |
| CN104845049B (en) | Preparation method of phosphorus-containing flame-retardant organic-inorganic hybrid silsesquioxane/epoxy resin hybrid material | |
| CN104356388B (en) | A kind of flame-retardant bismaleimide resin and preparation method thereof | |
| CN109232850A (en) | A kind of fire-retardant low thermal conductivity rigid polyurethane foam of aeroge modified heat resistant and preparation method thereof | |
| CN101597308A (en) | The preparation method of hexaaniline cyclotriphosphazene and halogen-free flame retardant epoxy resin composition | |
| CN106189092B (en) | A kind of fiber reinforcement flame-retarded light high-strength composite material and preparation method thereof | |
| CN105131330B (en) | The triazine flame retardant of 2,4,6 triphosphoric acid diethylester hydroxy methyl phenyloxy 1,3,5 and preparation method | |
| CN105348742B (en) | Compositions of thermosetting resin, prepreg and the laminate of the benzoxazine colophony containing melamine-type | |
| CN110256814A (en) | A kind of preparation method of the derivative modified fire retarding epoxide resin of DOPO containing piperazine structure | |
| CN105017771B (en) | A kind of bismaleimide resin composite material and preparation method thereof | |
| CN103073889A (en) | Flame retardant thermosetting resin and preparation method thereof | |
| CN105315492A (en) | Phosphorus silicon boron fire retardant based on cage-shaped silsesquioxane and preparation method thereof | |
| CN106496476B (en) | A kind of Effect of Organosilicon-modified Phenol-formaldehyde Resin and its application | |
| CN106751469A (en) | A kind of fluorine titanium Hybrid fire retardant and preparation method and application | |
| CN108203519A (en) | Alpha zirconium phosphate modified flame-retardant agent and its preparation method and application | |
| CN107663278B (en) | A kind of epoxy resin highly effective flame-retardant agent dispersing liquid and preparation method thereof | |
| CN106854370B (en) | A kind of supermolecule flame-proof silicon rubber and preparation method thereof | |
| CN106995673A (en) | A kind of low-gravity composite heat-conducting insulating cement and preparation method thereof | |
| CN109265481B (en) | Fluorine-rich flame retardant, preparation method thereof and flame-retardant epoxy resin modified by fluorine-rich flame retardant | |
| CN104371108B (en) | A kind of non-halogen non-phosphate Silicone-containing Flame Retardant and preparation method thereof | |
| CN106519583B (en) | A kind of halogen-free flameproof hand pasting forming composition epoxy resin and preparation method thereof | |
| CN106220665B (en) | Expansion type flame retardant of star-like pyrrolotriazine derivatives and preparation method thereof | |
| CN102321246B (en) | Polyborazine ceramic precursor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |