CN108864475A - A kind of silicon-phospha flame retarded rigid foam of polymers and preparation method thereof - Google Patents
A kind of silicon-phospha flame retarded rigid foam of polymers and preparation method thereof Download PDFInfo
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- CN108864475A CN108864475A CN201810815491.3A CN201810815491A CN108864475A CN 108864475 A CN108864475 A CN 108864475A CN 201810815491 A CN201810815491 A CN 201810815491A CN 108864475 A CN108864475 A CN 108864475A
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- silicon
- fire
- colloidal sol
- retardant
- phosphaization
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- 239000006260 foam Substances 0.000 title claims abstract description 56
- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000003063 flame retardant Substances 0.000 claims abstract description 58
- 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 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 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 16
- 235000019441 ethanol Nutrition 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims description 13
- -1 alkoxy silane Chemical compound 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000004364 calculation method Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 238000002803 maceration Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 150000003606 tin compounds Chemical class 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 2
- 239000000779 smoke Substances 0.000 abstract description 5
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229920005830 Polyurethane Foam Polymers 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 9
- 239000011496 polyurethane foam Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004786 cone calorimetry Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002323 Silicone foam Polymers 0.000 description 1
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-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
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 231100000734 genotoxic potential Toxicity 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000013514 silicone foam Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of fire-retardant colloidal sol of silicon-phosphaization for handling rigid polymer foam, and the fire-retardant colloidal sol contains two kinds of silicon, phosphorus elements.The fire-retardant colloidal sol is made by the reaction of two class precursor compounds；The two classes precursor compound is respectively：（1）Silane coupling agent with certain structure feature,（2）Contain DOPO primitive structure and the DOPO derivative that can be chemically bonded with silane coupling agent.The offer source object of the element silicon is alkoxy one type of silane coupling agent RxSi（OR´）y；Wherein R is the alkyl containing unsaturated functional group, and R ' is methyl or ethyl, x=1-2, y=2-3；The offer source substance of the P elements is the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and its corresponding derivative that can be reacted with the silane coupling agent.The present invention reduces about 69% than the smoke creating rate of regular-type foam.
Description
Technical field
The present invention relates to flame-retardant polymer foams, and in particular to a kind of silicon for handling rigid polymer foam-phosphaization resistance
Fire colloidal sol and its preparation method and application.
Background technique
Foam of polymers is the big porous material of a kind of light weight, specific strength, is widely used in as heat-insulating material daily
Life neutralizes industry, military field, especially extensive in exterior walls of buildings heat preservation and the application of pipe insulation field.Foam of polymers is same
When also have the characteristics that have sound insulation, shockproof, electrical isolation, weather-proof, solvent resistant, however since they have greatly specific surface area category
In easily combustible material, if people's security of the lives and property can be caused greatly to threaten by not doing effective flame retardant treatment.
There are three types of the flame retardant treatment mode of polymer is usual：Inherent flame retardant, additive flame retardant, surface treatment are fire-retardant.Essence
Fire-retardant also referred to as structural type is fire-retardant（Contain the structure with anti-flammability in the chain link or side group end group of macromolecular chain）, such as utilize resistance
Combustible polyether glycol produces resistance combustion polyurethane foam as raw material.Although however, can obtain so more stable anti-flammability but
It is that cost is too high, and synthesis technology is complicated.Additive flame retardant such as phosphorus-nitrogen containing flame retardant, hydridization filler really can be very big
Improve flame retardance of polymer and thermal stability in degree, but often mechanical property is generated since its additive amount is excessive bad
It influences.It is surface-treated a kind of one of the mode of the fire-retardant raising flame retardant effect for being energy maximal efficiency, material essential nature is influenced
It is smaller, it is applied in the field of surface treatment of fiber, timber, foam, but there is also process flow complexity to be not easy practical behaviour
The disadvantages of making.
With hard polyurethane foams（RPUF）For, people commonly use halogenated phosphate to reach ideal flame retardant effect
Based flame retardant handles RPUF, and P elements and halogens are used in compounding and are proved to have apparent synergistic effect, poly- to highly effective flame-retardant
The purpose of urethane rigid foam.Such as three（2- chloroethyl）Phosphate（TCEP）, tricresyl phosphate（Bis- chloro isopropyl of 1,3-）Ester
（TDCPP）And three (the chloro- 2- propyl of 1-) phosphoric acid (TCPP).However, such fire retardant containing halogens is deposited when in use
In genotoxic potential, human health and pollution environment are threatened.Therefore " green " fire retardant for seeking halogen-free environment-friendly type replaces halogen resistance
Firing agent becomes the direction that researchers make great efforts.
Silicon systems compound has good thermal stability and certain anti-flammability, it is considered to be environment protection additive；Silicon member
The fire retardant mechanism of element is usually solid phase fire retardant mechanism, and silicon-containing compound can be generated silica by thermal decomposition and be attached to burning matrix
Surface.However single use element silicon flame retardant effect is unsatisfactory, has document report to show, the fire-retardant need of single element silicon
Want longer self-extinguishing time.Phosphorus flame retardant can promote matrix to be dehydrated into charcoal, equally exist that independent additive effect is bad to ask
Topic is used generally only as the acid source of intumescent system.
Summary of the invention
The problem to be solved in the present invention is against the above deficiency, to provide a kind of silicon-phospha for handling rigid polymer foam
Change fire-retardant colloidal sol and its preparation method and application, realizes following goal of the invention：When shortening the self-extinguishing without fire of rigid polymer foam
Between, it reduces smog and generates rate, to obtain the rigid polymer foam of excellent fireproof performance.
For achieving the above object, using following technical scheme：
A kind of fire-retardant colloidal sol of silicon-phosphaization handling rigid polymer foam, the fire-retardant colloidal sol contain two kinds of silicon, phosphorus elements.
The fire-retardant colloidal sol is made by the reaction of two class precursor compounds；The two classes precursor compound is respectively：
（1）Silane coupling agent with certain structure feature,（2）Containing DOPO primitive structure and chemical bond can occur with silane coupling agent
The DOPO derivative of conjunction.
The offer source object of the element silicon is alkoxy one type of silane coupling agent RxSi（OR´）y；Wherein R is to contain unsaturation
The alkyl of functional group, R ' are methyl or ethyl, x=1-2, y=2-3.
The offer source substance of the P elements is 9, the 10- dihydro-9-oxy that can be reacted with the silane coupling agent
Miscellaneous -10- phospho hetero phenanthrene -10- oxide and its corresponding derivative.
A kind of preparation method for the fire-retardant colloidal sol of silicon-phosphaization handling rigid polymer foam, it is fire-retardant molten by silicon-phosphaization
The presoma DOPO derivative and alkoxy silane of glue carry out cohydrolysis in acid condition according to a certain percentage, and obtaining has resistance
The silicon of the fuel efficiency fruit-phospha hydrosol；The acid condition：PH 2-5 is controlled, is mentioned by acidic materials such as hydrochloric acid, acetic acid or sulfuric acid
For.
The preparation method includes synthesis silicon-phosphorus hybrid collosol step；
Synthesis silicon-phosphorus the hybrid collosol：Presoma DOPO derivative is dissolved with alcohols solvent, and mixed with alkoxy silane
It closes uniformly, was added drop-wise in hydrolyzation system at a slow speed with 0.5-1.5 hours, hydrolyzed under the conditions of room temperature is to 20-70 DEG C after being added dropwise to complete
Reaction 15-60 minutes, with organic base neutralization reaction, obtains being dissolved in the fire-retardant colloidal sol of silicon-phosphaization in alcohol；
The organic base：Preferably triethylamine, the alcohol：Preferably ethyl alcohol.
The hydrolyzation system is：Ethyl alcohol is uniformly mixed under the conditions of 25-50 DEG C with the water of calculation amount, obtains hydrolysis body
System；The water of the calculation amount：Water required for hydrolysis, mole of water and alkoxy are provided with the aqueous hydrochloric acid solution of PH=2-4
Than being 0.5-1:1.
The mass ratio of the presoma DOPO derivative and alkoxy silane is: 9:1-1:9.
The mass ratio of the presoma DOPO derivative and alkoxy silane is: 8:2-3:7, at fire-retardant colloidal sol obtained
The rigid polymer foam of reason：Oxygen index (OI) is more than 24%.
The mass ratio of the presoma DOPO derivative and alkoxy silane is: 7：3, fire-retardant colloidal sol processing obtained
Rigid polymer foam：Oxygen index (OI) is 29%, rises to 800 DEG C by room temperature with the heating rate of 10 DEG C/min in air atmosphere
Under the conditions of thermally decomposed after residual heavy percentage up to 65.5%, put out from fire, smog generation rate SPR value is 0.07m2/s。
A kind of application for the fire-retardant colloidal sol of silicon-phosphaization handling rigid polymer foam, the application include preparing silicon-phosphorus
Hydridization flame retarded rigid foam of polymers step；
Described prepares silicon-phospha flame retarded rigid foam of polymers：Organic tin compound is selected to add as curing catalysts
Enter fire-retardant sol system and stir evenly obtained maceration extract, under vacuum conditions, non-antiflaming rigid polymer foam is put into
In maceration extract, impregnates 15-30 minutes, be then centrifuged for removing extra solution, baking and curing 1.5-2.5 is small under the conditions of 80-120 DEG C
When, obtain silicon-phospha flame retarded rigid foam of polymers；
Described prepares maceration extract：By the silicon-phosphorus hybrid collosol of the dissolution of preparation in ethanol, a certain amount of solidification catalysis is added
Agent is stirred 10-20 minutes；
The curing catalysts：For dibutyl tin dilaurate；The additional amount of the dibutyl tin dilaurate is silicon-phospha
Change the 1%-4% of colloidal sol Solute mass.
Compared with prior art, technical solution of the present invention has the advantages that：
Silicon prepared by the present invention-phospha flame retarded rigid foam of polymers（SiP-RPUF）, 2s is lighted in flame flame envelope, it is then fast
Speed removes flame, and the used time independently extinguished is only 0.5s, a small amount of smoke；The oxygen index (OI) of SiP-RPUF of the present invention is up to 19.5-
29.1%.The present invention reduces about 69% than the smoke creating rate of regular-type foam；Taper calorimetric test display heat release rate peak
Value PHRR reduces 65%；Thermogravimetric analysis shows that carbon yield is increased to 65.5% from 10%.
Detailed description of the invention
Fig. 1 is the burn test results figure of 10 SiP-RPUF of embodiment.
Specific embodiment
A kind of preparation method for the fire-retardant colloidal sol of silicon-phosphaization for handling rigid polymer foam of embodiment 1
Include the following steps：
DOPO of the present invention is：9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the VTMS are：Ethylene
Base trimethoxy silane, the MTMS are：Methyltrimethoxysilane.
Step 1, synthesis DOPO-VTMS
The DOPO-VTMS：For the DOPO derivative synthesized by DOPO, VTMS.
By 0.2mol DOPO（43.2g）, 200ml toluene, 0.21mol VTMS（31.08g）It is added to three mouthfuls of 500ml
In bottle；Under nitrogen protection, mechanical stirring, condensing reflux mix raw material adequately with solvent, and specific mixing step is as follows：Make
Nitrogen is full of triangular flask, so that entire reaction system is increased the temperature to 80 DEG C, dissolves solid DOPO sufficiently by mechanical stirring
In a solvent, mixing time about 1 hour.
After DOPO dissolution, by 0.2g azodiisobutyronitrile（AIBN）It is dissolved in 50 milliliters of toluene, under the conditions of 80 DEG C
It is added drop-wise in there-necked flask at a slow speed, 2 hours this process used times.
The temperature for keeping reaction system is 80 DEG C, and mixing liquid is cooled to room temperature filtering after the reaction was continued 18 hours, is subtracted
Solvent is distilled off in pressure, is finally placed in vacuum drying oven further except solvent, obtains pale yellow transparent thick liquid, as
DOPO-VTMS。
Step 2, synthesis silicon-phosphorus hybrid collosol
Ethyl alcohol 20g, calculation amount water be added to single port bottle, under the conditions of 40 DEG C be uniformly mixed, obtain hydrolyzation system；The calculating
The water of amount：The molar ratio of water required for aqueous hydrochloric acid solution offer hydrolysis with PH=3, water and alkoxy is 0.8:1.
DOPO-VTMS prepared by the step 1 of calculation amount is dissolved with 20g ethyl alcohol and is uniformly mixed with MTMS, then with 1h
Duration is added drop-wise in hydrolyzation system at a slow speed, is continued hydrolysis 30 minutes under the conditions of 40 DEG C after being added dropwise to complete, is eventually adding meter
In the triethylamine of calculation amount and hydrochloric acid, obtain dissolving silicon-phosphorus hybrid collosol in ethanol, abbreviation SiR-DOPO, Solute mass
Score is 50%.
The total amount of DOPO-VTMS, MTMS are 20g in above-mentioned steps, and the mass ratio of presoma MTMS and DOPO-VTMS are 1:
9。
The triethylamine of above-mentioned calculation amount：HCl contained in the hydrochloric acid of pH=3 of the additional amount and addition of triethylamine etc. rubs
You.
The fire-retardant colloidal sol of silicon-phosphaization of above-mentioned processing rigid polymer foam is in preparing flame retarded rigid foam of polymers
Application：
Silicon-phosphorus the hybrid collosol of dissolution prepared by step 2 in ethanol（SiR-DOPO）, a certain amount of tin dilaurate two is added
Butyl tin mixes 15 minutes as curing catalysts, magnetic agitation, obtains maceration extract；
A certain amount of dibutyl tin dilaurate：The additional amount of dibutyl tin dilaurate is SiR-DOPO Solute mass
2%；
Under vacuum conditions, non-antiflaming hard polyurethane foams are put into above-mentioned maceration extract, impregnate 20 minutes, is then centrifuged for
Extra solution is removed, baking and curing 2 hours under the conditions of 100 DEG C finally obtain silicon-phospha flame retarded rigid polyurethane foams
（SiP-RPUF）.
Embodiment 2
It is same as Example 1, the mass ratio of MTMS and DOPO-VTMS in 2 synthesis silicon-phosphorus hybrid collosol is only changed the step, is carried out
Embodiment 2-9；
The mass ratio of the MTMS and DOPO-VTMS that use in embodiment 2-9 are as shown in table 1；
Table 1
The combustion test of 10 SiP-RPUF of embodiment
By untreated hard polyurethane foam and SiP-RPUF under the conditions of lighting on an equal basis, by the sample having a size of 10*10*10mm
Block lights 2s in flame flame envelope, then removes rapidly flame；Observe the aerial self-extinguishment situation of sample block, concrete condition such as Fig. 1
It is shown.
Test one group：The combustion case of untreated hard polyurethane foam and aerial self-extinguishment situation；
Test two groups：The combustion case of the SiP-RPUF of embodiment 3 and aerial self-extinguishment situation；
It can first be found out by Fig. 1, test one group：Untreated hard polyurethane foam is ignited rear vigorous combustion, in flame flame envelope
It lights 2s and leaves flame, 4-10s has open fire；A large amount of penetrating odor smog are released, fire-spreading property is extremely strong, combustion process
Continue 12s until sample is all burnt into residue.Test two groups：2s, which is lighted, in flame flame envelope leaves flame, flame when 2.5s
It is autonomous to extinguish；As it can be seen that it is only 0.5s that the SiP-RPUF of embodiment 3, which leaves the used time independently extinguished after flame, and only few
Smoke phenomenon is measured, illustrates that SiP-RPUF of the present invention does not have fire-spreading property, and there is suppression cigarette effect.
Then oxygen index (OI) test, test result such as table 2 have been done for the hard polyurethane foam of the processing of different phosphate silicon ratio
It is shown：
Table 2
As it can be seen that by silicon-phospha flame-retardant impregnating liquid, treated that foam oxygen index has different degrees of raising, wherein working as phosphorus
When silicon ratio is 3/7, oxygen index (OI) is up to 29.1%.
It is worth noting that not using the oxygen index (OI) of the neat silicone foam handled and the foam of pure DOPO-VTMS processing
Height, respectively 19.7% and 22.2%.
Embodiment 3 is preferred embodiment.
11 taper thermometric analysis of embodiment
Foam of polymers and pure RPUF, neat silicone, pure DOPO-VTMS to embodiment 3 handle to obtain foam of polymers,
It is analyzed by cone calorimetry, obtains that the results are shown in Table 3；
Table 3
The data analyzed by cone calorimetry are as shown in table 3：The duration of ignition（TTI）, heat release rate peak value（PHRR）,
Reach the time of exothermic peak（TTPHRR）, total heat release（THR）, flame growth rate (FIGRA=THRR/TTHRR), effectively combustion
Heat (EHC), mass loss rate（MLR）, residual rate.
The smoke creating rate of 3 foam of polymers of embodiment（SPR）Value is 0.07m2/ s, the smog than pure foam sample produce
Raw 0.22 m of rate2/ s is compared, and smog, which generates rate, reduces 68%.
The PHRR value of 3 foam of polymers of embodiment significantly reduces, from the 235kW/m of pure foam2It is reduced to 80.69kW/m2。
The FIGRA value of 3 foam of polymers of embodiment reduces 76.9% than pure foam；The ratio of 3 foam of polymers of embodiment is pure
The SPR of foam reduces about 69%, greatly reduces smog bring in practical fire and threatens.Combustion residue rate is by pure foam
16% be increased to the 52% of SiP-RPUF (7-3).It was found that utilizing the HRR value of neat silicone and pure the DOPO-VTMS RPUF handled
Also it decreases, respectively 145.45kW/m2And kW/m2；It is apparent that not as good as the flame retardant effect after silicon-phosphorus collaboration.
To sum up, preparation process of the present invention has obtained silicon-phospha of thermostabilization height, good flame retardation effect, excellent in mechanical performance
Flame retarded rigid polyurethane foams compound（SiP-RPUF）；When the ratio of DOPO-VTMS and neat silicone is 3：Silicon-phosphorus collaboration when 7
Effect be optimal.
The ratio of embodiment 3, DOPO-VTMS and neat silicone is 3：7, duration of ignition 6s, heat release rate peak value are
80.69 kW/m2, the time for reaching exothermic peak is 37s, and total heat is released to 14.8 kJ/m2, flame growth rate is 2.18 kW/
s·m2, active combustion heat is 13.47 MJ/kg, and mass loss rate is 0.081 g/s, residual rate 52%.
SiP-RPUF prepared by the present invention has excellent self-extinguishing without fire, and self-extinguishing time is only 0.5s, and oxygen index (OI) is
29%, heat release rate peak value PHRR are 80.69kW/m2 , smog generate rate SPR peak value reduced about compared with pure foam
69%, therefore the present invention substantially increases the fire safety of RPUF.
In addition to specified otherwise, percentage of the present invention is mass percent, and the ratio is mass ratio.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
It, for those skilled in the art, still can be with although describing the invention in detail with reference to the foregoing embodiments
It modifies the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.It is all
Within the spirit and principles in the present invention, any modification, equivalent replacement, improvement and so on should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of fire-retardant colloidal sol of silicon-phosphaization for handling rigid polymer foam, it is characterised in that：The fire-retardant colloidal sol contains
Two kinds of silicon, phosphorus elements.
2. a kind of fire-retardant colloidal sol of silicon-phosphaization for handling rigid polymer foam according to claim 1, feature exist
In：The fire-retardant colloidal sol is made by the reaction of two class precursor compounds；The two classes precursor compound is respectively：（1）Tool
There is the silane coupling agent of certain structure feature,（2）It can be chemically bonded containing DOPO primitive structure and with silane coupling agent
DOPO derivative.
3. a kind of fire-retardant colloidal sol of silicon-phosphaization for handling rigid polymer foam according to claim 1, feature exist
In：The offer source object of the element silicon is alkoxy one type of silane coupling agent RxSi（OR´）y；Wherein R is to contain unsaturated functional group
Alkyl, R ' be methyl or ethyl, x=1-2, y=2-3；
The offer source substance of the P elements be 9, the 10- dihydro-9-oxy that can react with the silane coupling agent it is miscellaneous-
10- phospho hetero phenanthrene -10- oxide and its corresponding derivative.
4. a kind of preparation method for the fire-retardant colloidal sol of silicon-phosphaization for handling rigid polymer foam, it is characterised in that：By silicon-phosphorus
The presoma DOPO derivative and alkoxy silane of the fire-retardant colloidal sol of hydridization carry out cohydrolysis in acid condition according to a certain percentage,
Obtain the silicon-phospha hydrosol with flame retardant effect；The acid condition：PH 2-5 is controlled, by hydrochloric acid, acetic acid or sulfuric acid etc.
Acidic materials provide.
5. a kind of preparation method of fire-retardant colloidal sol of silicon-phosphaization for handling rigid polymer foam according to claim 4,
It is characterized in that：The preparation method includes synthesis silicon-phosphorus hybrid collosol step；
Synthesis silicon-phosphorus the hybrid collosol：Presoma DOPO derivative is dissolved with alcohols solvent, and mixed with alkoxy silane
It closes uniformly, was added drop-wise in hydrolyzation system at a slow speed with 0.5-1.5 hours, hydrolyzed under the conditions of room temperature is to 20-70 DEG C after being added dropwise to complete
Reaction 15-60 minutes, with organic base neutralization reaction, obtains being dissolved in the fire-retardant colloidal sol of silicon-phosphaization in alcohol；
The organic base：Preferably triethylamine, the alcohol：Preferably ethyl alcohol.
6. a kind of preparation method of fire-retardant colloidal sol of silicon-phosphaization for handling rigid polymer foam according to claim 5,
It is characterized in that：The hydrolyzation system is：Ethyl alcohol is uniformly mixed under the conditions of 25-50 DEG C with the water of calculation amount, is hydrolyzed
System；The water of the calculation amount：Water required for aqueous hydrochloric acid solution offer hydrolysis with PH=2-4, water and alkoxy rub
Your ratio is 0.5-1:1.
7. a kind of preparation method of fire-retardant colloidal sol of silicon-phosphaization for handling rigid polymer foam according to claim 4,
It is characterized in that：The mass ratio of the presoma DOPO derivative and alkoxy silane is: 9:1-1:9.
8. a kind of preparation method of fire-retardant colloidal sol of silicon-phosphaization for handling rigid polymer foam according to claim 4,
It is characterized in that：The mass ratio of the presoma DOPO derivative and alkoxy silane is: 8:2-3:7, fire-retardant colloidal sol obtained
The rigid polymer foam of processing：Oxygen index (OI) is more than 24%.
9. a kind of preparation method of fire-retardant colloidal sol of silicon-phosphaization for handling rigid polymer foam according to claim 4,
It is characterized in that：The mass ratio of the presoma DOPO derivative and alkoxy silane is: 7：3, fire-retardant colloidal sol processing obtained
Rigid polymer foam：Oxygen index (OI) is 29%, rises to 800 DEG C by room temperature with the heating rate of 10 DEG C/min in air atmosphere
Under conditions of thermally decomposed after residual heavy percentage up to 65.5%, put out from fire, smog generation rate SPR value is 0.07m2/s。
10. a kind of application for the fire-retardant colloidal sol of silicon-phosphaization for handling rigid polymer foam, it is characterised in that：The application packet
It includes and prepares silicon-phospha flame retarded rigid foam of polymers step；
Described prepares silicon-phospha flame retarded rigid foam of polymers：Organic tin compound is selected to add as curing catalysts
Enter fire-retardant sol system and stir evenly obtained maceration extract, under vacuum conditions, non-antiflaming rigid polymer foam is put into
In maceration extract, impregnates 15-30 minutes, be then centrifuged for removing extra solution, baking and curing 1.5-2.5 is small under the conditions of 80-120 DEG C
When, obtain silicon-phospha flame retarded rigid foam of polymers；
Described prepares maceration extract：By the silicon-phosphorus hybrid collosol of the dissolution of preparation in ethanol, a certain amount of solidification catalysis is added
Agent is stirred 10-20 minutes；
The curing catalysts：For dibutyl tin dilaurate；The additional amount of the dibutyl tin dilaurate is silicon-phospha
Change the 1%-4% of colloidal sol Solute mass.
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