CN106749414B - A kind of phosphorous Silicone-containing Flame Retardant of response type and preparation method thereof - Google Patents
A kind of phosphorous Silicone-containing Flame Retardant of response type and preparation method thereof Download PDFInfo
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- CN106749414B CN106749414B CN201710024708.4A CN201710024708A CN106749414B CN 106749414 B CN106749414 B CN 106749414B CN 201710024708 A CN201710024708 A CN 201710024708A CN 106749414 B CN106749414 B CN 106749414B
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- flame retardant
- dopo
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- containing flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 66
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 24
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000004044 response Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 28
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- CWFXEZGOADTMDR-UHFFFAOYSA-N O1CCCC1.[Pt] Chemical compound O1CCCC1.[Pt] CWFXEZGOADTMDR-UHFFFAOYSA-N 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 239000012895 dilution Substances 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 229920002379 silicone rubber Polymers 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 7
- 230000000979 retarding effect Effects 0.000 abstract description 5
- 238000007259 addition reaction Methods 0.000 abstract description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 abstract 2
- 238000006757 chemical reactions by type Methods 0.000 abstract 1
- 125000005842 heteroatom Chemical group 0.000 abstract 1
- -1 siloxanes Chemical class 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 7
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- FCCRGBVYSYHQRQ-UHFFFAOYSA-N [ethenyl(dimethyl)silyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(C)C=C FCCRGBVYSYHQRQ-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- RJZNFXWQRHAVBP-UHFFFAOYSA-I aluminum;magnesium;pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Al+3] RJZNFXWQRHAVBP-UHFFFAOYSA-I 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OMUGFZNEOIWQOD-UHFFFAOYSA-N boric acid;zinc Chemical compound [Zn].OB(O)O OMUGFZNEOIWQOD-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses phosphorous Silicone-containing Flame Retardants of a kind of response type and preparation method thereof, the fire retardant is by 9, hydrogenation addition reaction preparation occurs for the miscellaneous -10- phospho hetero phenanthrene -10- oxide (DOPO) of 10- dihydro-9-oxy and tetramethyl divinyl disiloxane, the fire retardant contains active ethylene group, the highly effective reaction type fire retardant that can be used as silicon rubber uses, and flame retarding efficiency is high, no precipitation, small on mechanical property of materials influence, the flame retardant mechanism formula is for example shown below:
Description
Technical field
The present invention relates to phosphorous Silicone-containing Flame Retardants of a kind of response type and preparation method thereof, belong to fire proofing technical field,
It can be used for the highly effective flame-retardant of organic silicon rubber.
Background technique
Organic silicon rubber material is widely applied in industrial production and daily life, has certain burning self-extinguishment, but hinder
Combustion property is poor, and high flame retardancy silicon rubber is still the emphasis studied at present.Can be used at present silicon rubber fire retardant can be divided into it is halogen
Fire retardant and halogen-free flame retardants two major classes, since halogen containing flame-retardant has very big environmental protection pressure, many countries have forbidden making
With halogen-free anti-flaming silicon rubber is the hot spot of research.
The fire retardant that halogen-free anti-flaming silicon rubber uses mainly has inorganic fire retardants (such as magnesium aluminum hydroxide, hydration boric acid
Zinc), phosphorus flame retardant, nitrogenated flame retardant, phosphorus nitrogen expansion type combustion inhibitor etc..These fire retardants there are additive amounts big, flame retarding efficiency
Low, decomposition temperature is low, and the flame-proof silicon rubber specific gravity of preparation is larger, and the mechanical performance of material deteriorates seriously, and heat resistance is poor, together
When there are fire retardant be precipitated risk.Furthermore flame-proof silicon rubber, which also has, is used using platinum catalyst as fire retardant, this kind of fire-retardant
Agent is expensive, and is used alone, and effect is not obvious, and generally to compound phosphorus-nitrogen containing flame retardant.Efficient high heat resistance is without precipitation
Fire retardant is the emphasis of flame-proof silicon rubber research.
Summary of the invention
Overcome above-mentioned technical difficulty, the present invention has synthesized a kind of phosphorous Silicone-containing Flame Retardant of response type, which can be with
Solidification is crosslinked with silicon rubber, solves the problems, such as that fire retardant is easily precipitated, while phosphorus content is high, a small amount of addition can be played
Excellent flame retardant effect.
In order to realize above-mentioned technical goal, the invention adopts the following technical scheme:
The present invention provides a kind of phosphorous Silicone-containing Flame Retardant of response type, which has following chemical structural formula:
The preparation method of the fire retardant is: DOPO and its derivative under the action of catalyst, with tetramethyl divinyl two
The hydrogenated addition reaction preparation of siloxanes.
Wherein DOPO is a kind of new flame retardant intermediate: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
Its chemical structural formula are as follows:
The tetramethyl divinyl disiloxane chemical structural formula is as follows:
It is specific the preparation method is as follows:
1) by DOPO at 80 ~ 120 DEG C, 4 ~ 8 hours, preferably 4 hours are dried in vacuo at preferably 100 ~ 110 DEG C, drying is complete
It after complete DOPO or DOPO is completely dissolved using organic solvent A, is placed in autoclave, is passed through nitrogen protection and mechanical stirring
1 ~ 4 hour, preferably 2 ~ 3 hours；
2) catalyst is added in Xiang Shangshu autoclave, is warming up to 70 ~ 95 DEG C, preferably 80 ~ 90 DEG C, and continue to stir
0.2 ~ 0.8 hour, preferably 0.5 hour；
3) it is slowly dropped to after diluting divinyl endcapped siloxanes using organic solvent B in above-mentioned autoclave,
It is kept for 70 ~ 95 DEG C of temperature, preferably 80 ~ 90 DEG C, persistently stirs 20 ~ 25 hours, obtain product within preferably 24 hours；
4) it is cooled to room temperature, filters and is washed with toluene, 110 DEG C of vacuum drying, obtained faint yellow or white solid powder
End is the phosphorous Silicone-containing Flame Retardant of response type described in chemical structural formula (I).
Above-mentioned preparation method is related to a kind of hydrogenation addition reaction, to obtain single-ended vinyl target product, by diluted two
Vinyl tetramethyl disiloxane is slowly dropped in DOPO solution, while it is of the invention for controlling the molar ratio between reactant
It is crucial.DOPO phosphorus content with higher itself and thermal decomposition temperature, are a kind of efficient flame-retarding agents, and the present invention is by DOPO and tetramethyl
The reaction of base divinyl endcapped siloxanes prepares single-ended vinyl phosphorous Silicone-containing Flame Retardant, and because containing vinyl, therefore fire retardant has
Activity when being used for inflaming retarding high-temperature sulphurated siliastic, can be used as a kind of reactive flame retardant and be added in high-temperature silicon disulfide rubber,
The vinyl group that fire retardant contains can be reacted with end-vinyl silicon rubber, therefore compatibility is good, be influenced on the mechanical performance of material
Very little, while flame retardant effect is splendid.
Further, the present invention into autoclave be added dissolved by organic solvent A DOPO when, DOPO solution
Concentration is 0.5 ~ 2mol/L.It is preferred that 0.8 ~ 1.5mol/L, most preferably 1.0 ~ 1.2mol/L.
Further, organic solvent A of the present invention is isopropanol, dimethylformamide, at least one in dioxane
Kind.
Further, catalyst of the present invention be chloroplatinic acid aqueous isopropanol, wherein chloroplatinic acid mass fraction be 1%,
At least one of platinum-tetrahydrofuran complex, platinum-vinyl methyl siloxane complex compound.
The further heterolytic fission of phosphorus hydrogen bond on DOPO molecular structure can be enhanced in the use of catalyst, thus with tetramethyl diethyl
The reaction of alkenyl disiloxane, improves reaction rate and yield, shortens the reaction time.
Further, the additive amount of catalyst of the present invention is DOPO and tetramethyl divinyl disiloxane gross mass
0.05 ~ 0.5%, preferably 0.1 ~ 0.2%.
Further, the divinyl endcapped siloxanes dissolved by organic solvent B are being added into autoclave by the present invention
When, the concentration of the siloxanes are as follows: 0.1 ~ 1mol/L.It is preferred that 0.3 ~ 0.8mol/L, most preferably 0.4 ~ 0.5mol/L.
Further, organic solvent B of the present invention is at least one of toluene, dimethylbenzene, hexamethylene.
Further, the molar ratio of DOPO and tetramethyl divinyl disiloxane of the present invention are 1:0.8 ~ 1.2, excellent
Select 1:0.9 ~ 1.1.
The beneficial effects of the present invention are: the present invention to use DOPO, under the action of catalyst with tetramethyl divinyl two
The hydrogenated addition reaction of siloxanes prepares the phosphorous Silicone-containing Flame Retardant of response type, and the fire retardant phosphorus content is high, flame retarding efficiency is high, heat point
It is high to solve temperature, and the fire retardant contains active ethylene group, can be used as a kind of high temperature vulcanized type silicon of reactive flame retardant participation
Rubber it is flame-retardant modified, the preparation process of fire retardant of the invention has the advantages that purity is high, yield are high, preparation cost is low.
Specific embodiment
The technology of the present invention method is described further combined with specific embodiments below.But the present invention is not limited to
The embodiment of lower proposition.
The present invention provides a kind of phosphorous Silicone-containing Flame Retardant of response type, which has following chemical structural formula:
The right agent of the resistance is a kind of right agent of resistance of response type, can participate in the flame-retardant modified of high temperature vulcanizable silicone, fire-retardant
The vinyl that agent contains can be crosslinked with end-vinyl silicon rubber to react, and the consistency problem of fire retardant is solved, to material
Mechanical performance influences smaller.The fire retardant also can be applied in other organosilicon materials simultaneously, such as fluid silicone rubber is fire-retardant.
The present invention provides a kind of preparation methods 1 of the phosphorous Silicone-containing Flame Retardant of response type) by DOPO at 100 ~ 120 DEG C, it is excellent
It selects and is dried in vacuo 4 ~ 8h at 110 DEG C, preferably 4 hours, the DOPO chemical structural formula are as follows:
After the dry DOPO finished or DOPO is completely dissolved using organic solvent A, it is placed in autoclave, is passed through nitrogen
Gas shielded and mechanical stirring 1 ~ 4 hour, preferably 2 hours；
2) catalyst is added in Xiang Shangshu autoclave, is warming up to 70 ~ 95 DEG C, preferably 80 ~ 90 DEG C, and continue to stir
0.2 ~ 0.8 hour, preferably 0.5 hour；
3) it is slowly dropped to after diluting divinyl endcapped siloxanes using organic solvent B in above-mentioned autoclave,
Temperatures above is kept persistently to stir 20 ~ 25 hours；
4) using dry method is filtered, obtained faint yellow or white solid powder is that chemical structural formula (I) is described
The phosphorous Silicone-containing Flame Retardant of response type.
Embodiment 1
By 216g(1mol) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) dry 8 at 110 DEG C
Hour, it is placed in 5L autoclave, is passed through nitrogen protection, 1200mL n,N-Dimethylformamide, mechanical stirring 0.5 is added
Hour, by aqueous isopropanol (chloroplatinic acid mass fraction 1%) the merging autoclave of 0.8g chloroplatinic acid, 90 DEG C are warming up to, after
Continuous stirring 0.5 hour.The 204.6g(1.1mol that 2000mL toluene dissolves) divinyl tetramethyl disiloxane is slowly added dropwise
Into autoclave.At a temperature of 90 DEG C, the reaction was continued 24 hours, filters drying, obtains faint yellow or white solid powder,
The phosphorous Silicone-containing Flame Retardant of response type as of the present invention, yield 90%.
Embodiment 2
216g(1mol) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 4 hours dry at 100 DEG C, it sets
Enter in 5L autoclave, be passed through nitrogen protection, is added 1000mL1,4- dioxane, mechanical stirring 0.6 hour, by 0.4g platinum
(0) -1,3- divinyl -1,1,3,3- tetramethyl disiloxane complex compounds are placed in autoclave, are warming up to 80 DEG C, continue to stir
It mixes 0.5 hour.The 167.4g(0.9mol that 1500mL hexamethylene dissolves) divinyl tetramethyl disiloxane is slowly dropped to
In autoclave, at a temperature of 80 DEG C, the reaction was continued 20 hours, filters drying, obtains faint yellow or white solid powder, i.e.,
For the phosphorous Silicone-containing Flame Retardant of response type described in this explanation, yield 95%.
Embodiment 3
216g(1mol) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 4 hours dry at 110 DEG C, it sets
Enter in 5L autoclave, be passed through nitrogen protection, is added 1500mL isopropanol, mechanical stirring 0.5 hour, by 0.8g platinum-tetrahydro
Furans complex compound is placed in autoclave, is warming up to 85 DEG C, continues stirring 0.5 hour.By 1200mL xylene soluble
186g(1mol) divinyl tetramethyl disiloxane is slowly dropped in autoclave, and at a temperature of 85 DEG C, the reaction was continued
24 hours, drying is filtered, obtains faint yellow or white solid powder, as this explanation response type is phosphorous siliceous fire-retardant
Agent, yield 92%.
Embodiment 4
By 216g(1mol) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) dry 4 at 110 DEG C
Hour, it is placed in 5L autoclave, is passed through nitrogen protection, be added 1500mL isopropanol, mechanical stirring 0.8 hour, by 0.5g
Platinum (0) -1,3- divinyl -1,1,3,3- tetramethyl disiloxane complex compounds are placed in autoclave, are warming up to 90 DEG C, are continued
Stirring 0.5 hour.The 195.3g(1.05mol that 1200mL toluene dissolves) divinyl tetramethyl disiloxane is slowly dropped to
In autoclave, at a temperature of 90 DEG C, the reaction was continued 20 hours, filters drying, obtains faint yellow or white solid powder, i.e.,
For the phosphorous Silicone-containing Flame Retardant of response type described in this explanation, yield 88%.
Embodiment 5
By 216g(1mol) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) dry 4 at 105 DEG C
Hour, it is placed in 5L autoclave, is passed through nitrogen protection, be added 2000mL1,4- dioxane, mechanical stirring 0.5 hour,
By in 0.5g platinum-tetrahydrofuran complex merging autoclave, 80 DEG C are warming up to, stirring 0.4 hour is continued.By 1500mL bis-
The 204.6g(1.1mol of toluene dissolution) divinyl tetramethyl disiloxane is slowly dropped in autoclave, in 80 DEG C of temperature
Under degree, the reaction was continued 24 hours, filters drying, obtains faint yellow or white solid powder, as this explanation response type
Phosphorous Silicone-containing Flame Retardant, yield 87%.
Flame retardant property test: by 100g vinylsiloxane rubber (molecular weight is 60-80 × 104Da), two silicon nitrogen of 50g hexamethyl
Alkane is modified gas-phase silica (specific surface area 250m2/g), and adding fire retardant respectively is 10g, 15g, 20g, mixes in kneader
Uniformly after, be added 1.5g bis 25 vulcanizing agent, vulcanize 10min on 140 DEG C of vulcanizing presses, then in 200 DEG C of baking ovens it is secondary
Vulcanization 4 hours, test sample performance, such as table (1).
From the point of view of above experimental data, phosphorous Silicone-containing Flame Retardant of the present invention, flame retarding efficiency is high, to material
The influence of mechanical performance is smaller.Wherein two comprehensive performance of example is optimal, when fire retardant additive amount is 15 parts, flame retardant rating UL94V-
0。
Claims (5)
1. a kind of phosphorous Silicone-containing Flame Retardant of response type, it is characterised in that: the fire retardant has following chemical structural formula (I):
(I).
2. a kind of preparation method of the phosphorous Silicone-containing Flame Retardant of response type, it is characterised in that: the preparation method includes following step
It is rapid:
1) DOPO is dried in vacuo to 4 ~ 8h at 80 ~ 120 DEG C, after the dry DOPO finished is completely dissolved with organic solvent A, is set
In autoclave, it is passed through nitrogen protection and mechanical stirring 1 ~ 4 hour, the organic solvent A is ethyl alcohol, chloroform, diformazan
At least one of base formamide, dioxane, when the DOPO dissolved by organic solvent A is added into autoclave,
The concentration of DOPO solution is 0.5 ~ 2mol/L；
2) catalyst is added in Xiang Shangshu autoclave, is warming up to 70 ~ 95 DEG C, and continue stirring 0.2 ~ 0.8 hour；
3) it is slowly dropped to after diluting tetramethyl divinyl disiloxane using organic solvent B in above-mentioned autoclave,
The organic solvent B is at least one of toluene, dimethylbenzene, hexamethylene, tetramethyl divinyl disiloxane after dilution
Concentration be 0.1 ~ 1mol/L, keep 70 ~ 95 DEG C of temperature, persistently stir 20 ~ 25 hours；
4) it is cooled to room temperature, filters and is washed with toluene, is dried in vacuo, obtained faint yellow or white solid powder is chemistry
Structural formula (I)The phosphorous Silicone-containing Flame Retardant of the response type.
3. a kind of preparation method of the phosphorous Silicone-containing Flame Retardant of response type according to claim 2, it is characterised in that: described
Catalyst be chloroplatinic acid aqueous isopropanol, wherein chloroplatinic acid mass fraction be 1%, platinum-tetrahydrofuran complex, platinum (0) -1,
At least one of 3- divinyl -1,1,3,3- tetramethyl disiloxane complex compound.
4. a kind of preparation method of the phosphorous Silicone-containing Flame Retardant of response type according to claim 2, it is characterised in that: described
The additive amount of catalyst is the 0.05 ~ 0.5% of DOPO and tetramethyl divinyl disiloxane gross mass.
5. a kind of preparation method of the phosphorous Silicone-containing Flame Retardant of response type according to claim 2, it is characterised in that: described
The molar ratio of DOPO and tetramethyl divinyl disiloxane is 1:0.8 ~ 1.2.
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| CN111363339A (en) * | 2018-12-26 | 2020-07-03 | 广东生益科技股份有限公司 | Phosphorus-silicon-containing flame retardant, preparation method thereof, flame-retardant resin composition, prepreg and metal-foil-clad laminate |
| CN112442077A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with reactive groups and preparation method and application thereof |
| CN112442073A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant and preparation method and application thereof |
| CN112876508A (en) * | 2020-10-29 | 2021-06-01 | 广东广山新材料股份有限公司 | Reactive phosphorus-silicon synergistic flame retardant, polymeric phosphorus-silicon synergistic flame retardant, and preparation method and application thereof |
| CN114031779B (en) * | 2021-11-01 | 2023-02-28 | 兰州瑞朴科技有限公司 | Phosphorus-containing ladder-shaped polysiloxane, preparation method thereof and application of phosphorus-containing ladder-shaped polysiloxane as flame-retardant synergist |
| CN116515041A (en) * | 2023-03-11 | 2023-08-01 | 北京工商大学 | Phosphaphenanthrene/siloxane double-based macromolecular flame retardant and preparation method thereof |
| CN116875158A (en) * | 2023-04-06 | 2023-10-13 | 南雄市双溪丽盈化工涂料有限公司 | Flame-retardant PE unsaturated polyester coating and synthesis process thereof |
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