CN105199384A - Transparent flame-retardant benzoxazine nanocomposite and preparation method thereof - Google Patents
Transparent flame-retardant benzoxazine nanocomposite and preparation method thereof Download PDFInfo
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- CN105199384A CN105199384A CN201510602647.6A CN201510602647A CN105199384A CN 105199384 A CN105199384 A CN 105199384A CN 201510602647 A CN201510602647 A CN 201510602647A CN 105199384 A CN105199384 A CN 105199384A
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- benzoxazine
- zirconium phosphate
- alpha zirconium
- acetone
- retardant
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000003063 flame retardant Substances 0.000 title claims abstract description 57
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 22
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 108
- 239000000463 material Substances 0.000 claims abstract description 79
- 239000000178 monomer Substances 0.000 claims abstract description 76
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 139
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 107
- 239000007788 liquid Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 31
- 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 28
- 229930185605 Bisphenol Natural products 0.000 claims description 26
- 230000001588 bifunctional effect Effects 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 238000007711 solidification Methods 0.000 claims description 25
- 230000008023 solidification Effects 0.000 claims description 25
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 19
- 229910052726 zirconium Inorganic materials 0.000 claims description 19
- 241000446313 Lamella Species 0.000 claims description 15
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 238000000703 high-speed centrifugation Methods 0.000 claims description 7
- 239000006249 magnetic particle Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 7
- 238000011160 research Methods 0.000 abstract description 4
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 15
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000003610 charcoal Substances 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005352 clarification Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004786 cone calorimetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
-
- 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
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a transparent flame-retardant benzoxazine nanocomposite and a preparation method thereof. The transparent flame-retardant benzoxazine nanocomposite is prepared from 75-99 parts of benzoxazine resin and 1-25 parts of ionized-state layered alpha-zirconium phosphate. The ratio of the slice layer diameter to the slice layer thickness of the ionized-state layered alpha-zirconium phosphate ranges from 50 to 1,000. According to the transparent flame-retardant benzoxazine nanocomposite, the ring opening polymerization temperature of benzoxazine monomers is reduced on the basis of guaranteeing the good overall property of the nanocomposite, meanwhile, flame retardation of the benzoxazine resin is improved, multiple properties of thermosetting resin can be optimized, and a new research thought is provided for modification of the thermosetting resin. The transparent flame-retardant benzoxazine nanocomposite can be applied to occasions with high requirements for transparency and flame retardation of the material.
Description
Technical field
The present invention relates to fire-retardant benzoxazine nano composite material of a kind of transparent type and preparation method thereof, belong to new functional macromolecule material and preparation field thereof.
Background technology
Benzoxazine (PBa) is a class novel hot setting resin, be heated or ring-opening polymerization preparation (JournalofPolymerSciencePartA:PolymerChemistry under catalyst action through benzoxazine monomer (Ba), 2011,49:4213-4220; RSCAdvances, 2015,5:47284-47293.).Benzoxazine monomer by phenols, primary amine and paraformaldehyde or formaldehyde through Mannich Reactive Synthesis.By changing the structure of primary amine and phenolic compound, dissimilar benzoxazine monomer can be prepared, and then obtain the benzoxazine colophony material (US7517925B2 of different performance feature; CN101578332A).Without small molecules release in ring opening polymerisation process, resin shrinkage rate is practically negligible, and product size is stablized.The advantage such as benzoxazine colophony has good thermal stability, intensity is high, modulus is large and specific inductivity is little, is applicable to engineering plastics and electrically insulating material (US2011/0112235A1).In numerous benzoxazine colophony, bisphenol A-type benzoxazine has best over-all properties and nominal price, has obtained marketization application.But bisphenol A-type benzoxazine is incendivity in atmosphere, and with a large amount of black dense smoke in combustion processes.Along with people to numerous areas such as living environment safety and electronic apparatuss to the demand of fire retardant material, the combustibility of bisphenol A type epoxy resin seriously limits its application development.
At present, Dui benzoxazine colophony carries out fire-retardant method has: (1) directly adds halogenated flame retardant, phosphonium flame retardant, phosphorous-nitrogen combustion inhibitor or siliceous fire-retardant in benzoxazine colophony; (2) the Xin type benzoxazine monomer (US8058362B2 containing ignition-proof element (halogen, phosphorus, nitrogen or silicon) is designed and synthesized; ).Halogenated flame retardant can discharge corrodibility toxic gas in combustion processes, has great damage to human body and environment.The structure such as-P-O-,-P-C and-P=O in phosphorous and phosphorus-nitrogen combustion inhibitor, the groups such as-the C-C-in this body structure of relative polymer and-C-O, thermal stability poor (JournalofAppliedPolymerScience, 2008,110:2413 – 2423).Therefore, in macromolecular material, the thermal stability that phosphor-containing flame-proof structure significantly can reduce material is introduced.The design of Xin type benzoxazine monomer and synthesis, can strengthen the production cycle of resin material, increases the production cost of resin matrix.
Nanoparticle, while raising macromolecular material flame retardant properties, often also can improve the thermal stability of material.But nanoparticle height interfacial energy makes it very easily reunite, be difficult to reach good distribution in resin matrix, thus affect material property.For addressing this problem, and considering the raising of Flame Retardancy energy, usually adopting P contained compound to carry out organically-modified to nanoparticle.Modified through organic phosphorus compound, when nanoparticle addition is larger, although make macromolecular material flame retardant properties be improved, the thermal stability (MaterialsChemistryandPhysics of material can be reduced, 2014,146:354-362).
The present invention overcomes the defect that organic phosphonium flame retardant reduces macromolecular material thermal stability, consider the high restriction in the application of benzoxazine monomer polymerization temperature simultaneously, adopt inorganic phosphorated laminar nano particle Dui benzoxazine colophony to carry out flame-retardant modified, and reduce benzoxazine monomer curing reaction temperature.Inorganic phosphorated laminar nano particle both can keep the flame retardant properties of phosphoric, had again good thermal stability, and acidic-group can catalysis benzoxazine monomer ring-opening reaction simultaneously.Flame retardant type benzoxazine nano composite material prepared by the method has the good transparency, can meet the requirement of the field such as electronic apparatus, space flight and aviation to flame retardant type benzoxazine performance and outward appearance.
Summary of the invention
The application prepares the fire-retardant benzoxazine colophony material of transparent type by inorganic phosphorated laminar nano particle, this material has good thermal stability, high strength and Young's modulus and good flame retardant properties, can meet electronic apparatus and field of aerospace to the requirement of performance resins material.In the present invention simultaneously, inorganic phosphorated laminar nano particle significantly can reduce the solidification value of benzoxazine monomer, and then reduces forming materials processing temperature, save energy, reduces material produce cost.
Main purpose of the present invention is for prior art Problems existing, provides the preparation method of a kind of transparent type fire-retardant benzoxazine nano composite material and this material.
Specifically, the fire-retardant benzoxazine nano composite material of transparent type provided by the invention, peels off state laminar alpha zirconium phosphate by 75 ~ 99 parts of benzoxazine colophonies and 1 ~ 25 part and forms.Wherein, the lamella diameter of alpha zirconium phosphate and thickness proportion are 50 ~ 1000.Phosphoric in alpha zirconium phosphate structure effectively can play and promote into charcoal effect in material combustion process; Alpha zirconium phosphate nanometer laminated structure can play physical barrier performance, delays or the transmission effect of oxygen and heat in blocks air, thus plays flame retardant effect; Acidic-group in alpha zirconium phosphate nanometer layer can form hydrogen bond action with benzoxazine monomer, Jiang Di oxazine ring cloud density, and then reduces benzoxazine monomer solidification value.
In the preparation method of the fire-retardant benzoxazine nano composite material of transparent type provided by the invention, utilize alpha zirconium phosphate constructional feature, adopt polyetheramine to carry out nanometer stripping to it, prepare alpha zirconium phosphate nanoscale twins; In conjunction with the performance characteristics peeling off state alpha zirconium phosphate nanoscale twins and benzoxazine monomer, to the two ultrasonic premix in acetone, vacuum rotary steam is except after desolventizing again, obtain benzoxazine monomer/stripping state alpha zirconium phosphate nanoscale twins mixture, benzoxazine monomer original position ring-opening polymerization under alpha zirconium phosphate nanoscale twins existent condition afterwards, obtains the fire-retardant benzoxazine colophony material of transparent type.-P-OH in alpha zirconium phosphate laminated structure has slightly acidic, simultaneously Zr
4+belong to Lewis acid, these two kinds of acid sitess all the ring-opening polymerization of Dui benzoxazine monomer can play katalysis, thus reduce benzoxazine monomer ring-opening polymerization temperature.According to maximum energy criterion benzoxazine monomer between alpha zirconium phosphate nanoscale twins after in-situ polymerization, cannot be rotated by molecule segment and nanoscale twins be assembled, and then ensure alpha zirconium phosphate lamella permanent nano-dispersed in benzoxazine colophony matrix, thus ensure the fire-retardant persistence of material.
Object of the present invention, is realized by following technology implementation.Wherein, described raw material number, except specified otherwise, is parts by weight.
First, the invention provides the fire-retardant benzoxazine nano composite material of a kind of transparent type, the fire-retardant benzoxazine nano composite material of this transparent type is peeled off state laminar alpha zirconium phosphate by 75 ~ 99 parts of benzoxazine colophonies and 1 ~ 25 part and is formed.
Wherein, lamella diameter and the thickness proportion of peeling off state laminar alpha zirconium phosphate are 50 ~ 1000.
Secondly, the present invention also provides the preparation method of the fire-retardant benzoxazine nano composite material of a kind of above-mentioned transparent type, and the method comprises the following steps:
(1) 1 ~ 25 part is peeled off state laminar alpha zirconium phosphate ultrasonic disperse in 5 ~ 200 parts of acetone;
(2) by 75 ~ 99 parts of benzoxazine monomer stirring and dissolving in 50 ~ 100 parts of acetone;
(3) slowly joined by the solution that step (2) obtains in the solution that step (1) obtains, ultrasonic disperse 30 ~ 120min obtains the mixture containing benzoxazine monomer/alpha zirconium phosphate afterwards;
(4) adopt Rotary Evaporators, the acetone contained in the mixture of benzoxazine monomer/alpha zirconium phosphate that 50 ~ 120 DEG C of gradient increased temperature removing steps (3) obtain, and remove air wherein;
(5) material that step (4) obtains is joined adopt in the pretreated glass mold of releasing agent, 100 ~ 130 DEG C of vacuum defoamations;
(6) material after deaeration to be transferred to together with mould in temperature programming baking oven 140 ~ 160 DEG C of solidifications 2 ~ 24 hours, 180 ~ 200 DEG C of solidifications 0 ~ 4 hour; In the process, benzoxazine monomer is open loop crosslinking reaction under the katalysis of stripping state laminar alpha zirconium phosphate, finally forms the transparent flame-retarding type nano composite material of benzoxazine colophony/alpha zirconium phosphate composition; After solidification process completes, after naturally cooling, obtain the fire-retardant benzoxazine nano composite material of described transparent type.
In aforesaid method, ultrasonic described in step (1) and step (3), its frequency be 20 ?40 hertz;
Benzoxazine monomer in step (2) is the bisphenol-f type benzoxazine monomer (one of structure a), in bisphenol A-type benzoxazine monomer (structure b), phenolphthalein type benzoxazine monomer (structure c) or thiodiphenol type benzoxazine monomer (structure d);
Temperature programming baking oven used in the present invention is the conventional instrument used, and the temperature programming baking oven that market can buy all can be used for the present invention.In the present invention, DHG-9075AD type temperature programming baking oven is used.
In addition, in the preparation method of the fire-retardant benzoxazine nano composite material of above-mentioned transparent type, peel off state laminar alpha zirconium phosphate by polyetheramine in acetone to alpha zirconium phosphate carry out intercalation organically-modified after obtain.Hydroxyl in polyetheramine structure in amido and alpha zirconium phosphate laminated structure can form very strong Hyarogen-bonding, and then polyetheramine molecule enters between alpha zirconium phosphate lamella, after ultrasonic disperse, makes alpha zirconium phosphate lamella in peeling off state completely.
In the preparation method of the fire-retardant benzoxazine nano composite material of the above-mentioned transparent type of the present invention, the preparation method peeling off state laminar alpha zirconium phosphate comprises the steps:
(1) by 5 ~ 15 parts of lamella diameters and thickness proportion be 5 ~ 20 alpha zirconium phosphate powder, under 40 ~ 100 hertz of ultrasound conditions, be distributed in 200 ~ 500 parts of acetone;
(2) weigh 10-50 part simple function group or bifunctional polyetheramine, be dispersed in 20-60 part acetone and obtain polyetheramine-acetone dispersion liquor;
(3) by the polyetheramine-acetone dispersion liquor of step (2), be added drop-wise in the solution that step (1) obtains within the scope of 25-60 minutes; 40 ~ 100 hertz of ultrasonic disperse 1 ~ 3h after dripping, magnetic particle stirs 6 ~ 24 hours, obtains alpha zirconium phosphate-polyetheramine-acetone stripping liquid;
(4) alpha zirconium phosphate-polyetheramine-acetone stripping liquid of supercentrifuge to step (3) is adopted to carry out centrifugal treating;
(5) by the upper liquid after step (4) centrifugal treating after 15000 ~ 25000 revs/min of high speed centrifugation process, next sediment is the stripping state laminar alpha zirconium phosphate that lamella diameter and thickness proportion are 50 ~ 1000.
Above-mentioned stripping state laminar alpha zirconium phosphate can be dispersed in acetone, dehydrated alcohol, toluene, benzene, DMF and NVP solvent after ultrasonic.
In preparation method's step of above-mentioned stripping state laminar alpha zirconium phosphate, the simple function group described in step (2) or bifunctional polyetheramine are the one below in structure (I), structure (II) or structure (III).
Wherein, in structure (I), x/y=0.1 ~ 9, molecular weight is 600 ~ 2000; In structure (II), x=2 ~ 35, molecular weight is 200 ~ 2000; In structure (III), x+z=1 ~ 6, y=2 ~ 40, molecular weight is 200 ~ 2000.
Centrifugation step speed described in step (4) is 5000-10000 rev/min;
The Structure and Properties test related in the embodiment of the present invention is carried out by the following method:
(1) solidification value: the initial curing temperature and the maximum cure rate corresponding temperature that adopt U.S. TA company Q20 type differential scanning calorimeter (DSC) test unit and monomer/alpha zirconium phosphate mixture.
(2) microtexture: adopt JEOLJSM-5900LV type scanning electron microscope (SEM) to analyze.Sample is gold-plated on vacuum coater, then observe on SEM instrument, make a video recording, obtain the micro-structure diagram of layer of charcoal after burning.
(3) thermal stability: adopt STA449F3 type thermal analyzer (NETZSCH) to test the thermostability of nano composite material respectively in air and nitrogen atmosphere.Range of measuring temp is room temperature ~ 800 DEG C, and temperature rise rate is 10 DEG C/min, and gas flow rate is 60mL/min.
(4) flame retardant properties: adopt UKFTTISO5660 technological standard to measure heat release rate and the smoke density of toughness reinforcing-fire retardant material, investigate the flame retardant properties of material.Toughening flame-proof type epoxy resin is made the thick model being respectively 100mm, 100mm, 3.2mm of length and width, cone calorimetry is tested.
Compared with the prior art the present invention, has following advantage:
(1) the fire-retardant benzoxazine nano composite material of transparent type provided by the invention, on the guarantee good over-all properties basis of material, reduce benzoxazine monomer ring-opening polymerization temperature, improve the flame retardant properties of benzoxazine colophony simultaneously, achieve the multiple performance optimization of thermosetting resin, for thermosetting resin modification improves new Research Thinking.
(2) research method provided by the invention can save energy consumption in benzoxazine colophony and Nano-composite materials process thereof, and then reduces material produce cost.Simultaneously, research method provided by the invention improves benzoxazine colophony thermal stability, extend benzoxazine colophony burning time, reduce benzoxazine colophony heat release rate and carbon monoxide and carbon dioxide releasing amount in combustion, improve benzoxazine colophony safety in utilization.
(3) in the fire-retardant benzoxazine nano composite material of transparent type provided by the invention, work the nanometer alpha zirconium phosphate reducing solidification value and improve flame retardant properties, for monolithic layer laminate structure, can be dispersed in benzoxazine colophony matrix, and with benzoxazine colophony matrix, there is good interface consistency, the fire-retardant persistence of material can be ensured.
(4) the fire-retardant benzoxazine nano composite material of transparent type provided by the invention, preparation process is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the DSC test curve of pure bisphenol A-type benzoxazine monomer described in bisphenol A-type benzoxazine monomer/alpha zirconium phosphate mixture described in embodiment 1 and comparative example 1;
Fig. 2 is material thermogravimetric test (TGA) curve in air atmosphere after solidification described in embodiment 1 and comparative example 1;
Fig. 3 is material thermogravimetric test (TGA) curve in nitrogen atmosphere after solidification described in embodiment 1 and comparative example 1;
Fig. 4 is the heat release rate-time curve obtained in the tapered calorimetric test of material after solidification described in embodiment 3 and comparative example 1;
Fig. 5 is the total burst size-time curve of carbon monoxide (CO) obtained in material tapered calorimetric test after solidification described in embodiment 3 and comparative example 1;
Fig. 6 is layer of charcoal (a) outside surface and (b) internal structure scanning electron microscope (SEM) photograph after the rear material combustion of solidification described in embodiment 3.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to scope.
Embodiment 1
By the alpha zirconium phosphate powder that 5 parts of lamella diameters and thickness proportion are 20, under 40 hertz of ultrasound conditions, be distributed in 200 parts of acetone, obtain alpha zirconium phosphate powder-acetone suspension liquid.Weigh the structure I type simple function group polyetheramine that 16 parts of molecular weight are 1000, be dispersed in 50 parts of acetone and obtain structure I type simple function group polyetheramine-acetone dispersion liquor.By structure I type simple function group polyetheramine-acetone dispersion liquor, be added drop-wise in 25 minutes in alpha zirconium phosphate powder-acetone suspension liquid.Drip rear 40 hertz of ultrasonic disperse 1h, magnetic particle stirs 24 hours, obtains alpha zirconium phosphate-structure I type simple function group polyetheramine-acetone stripping liquid.Whizzer 10000 revs/min of rotating speeds carry out centrifugal treating to alpha zirconium phosphate-structure I type simple function group polyetheramine-acetone stripping liquid.Alpha zirconium phosphate-structure I type simple function group polyetheramine-acetone stripping liquid, after the process of 10000 revs/min, whizzer, is divided into a small amount of sediment bottom clarification upper liquid and centrifuge tube.By the upper liquid after centrifugal treating after 20000 revs/min of high speed centrifugation process, next sediment is the laminar alpha zirconium phosphate that molecular weight is the structure I type simple function group polyetheramine stripping of 1000.
3 parts of molecular weight are that alpha zirconium phosphate 40 hertz of ultrasonic disperse of the structure I type simple function group polyetheramine stripping of 1000 are in 15 parts of acetone.97 parts of bisphenol A-type benzoxazine monomers are dissolved in 100 parts of acetone.Then alpha zirconium phosphate/acetone dispersion liquor said structure I type simple function group polyetheramine peeled off and bisphenol A-type benzoxazine monomer/acetone soln mixing, and 40 hertz of ultrasonic disperse 30min.Adopt Rotary Evaporators, remove acetone under 50 DEG C, 80 DEG C and 120 DEG C of three temperature stage, and remove the air in bisphenol A-type benzoxazine monomer/stripping state alpha zirconium phosphate mixture.Being joined by bisphenol A-type benzoxazine monomer/stripping state alpha zirconium phosphate mixture adopts in the pretreated glass mold of releasing agent, in 100 DEG C of vacuum drying ovens after deaeration, mould and bisphenol A-type benzoxazine monomer/stripping state alpha zirconium phosphate mixture are transferred in temperature programming baking oven.160 DEG C solidify 24 hours.In the process, bisphenol A-type benzoxazine monomer is open loop crosslinking reaction under alpha zirconium phosphate katalysis, forms bisphenol A-type benzoxazine colophony/alpha zirconium phosphate nano composite material.After solidification process completes, naturally cooling, obtains transparent type fire-retardant bisphenol A-type benzoxazine nano composite material.
Described in bisphenol A-type benzoxazine monomer described in embodiment 1/stripping state alpha zirconium phosphate mixture and comparative example 1, the DSC test curve of pure bisphenol A-type benzoxazine monomer is shown in accompanying drawing 1.Accompanying drawing 2 and accompanying drawing 3 are respectively thermogravimetric test (TGA) curve in air and nitrogen atmosphere of bisphenol A-type benzoxazine colophony described in transparent type fire-retardant bisphenol A-type benzoxazine nano composite material described in embodiment 1 and comparative example 1.Can see from accompanying drawing 1, alpha zirconium phosphate can make benzoxazine Open loop temperature significantly reduce, and obviously reduces maximum cure rate corresponding temperature.In accompanying drawing 2 and accompanying drawing 3, thermogravimetric curve shows, in air atmosphere and nitrogen atmosphere, alpha zirconium phosphate all can improve thermal stability and the high-temperature residual amount of benzoxazine colophony.
Embodiment 2
By the alpha zirconium phosphate powder that 15 parts of lamella diameters and thickness proportion are 5, under 100 hertz of ultrasound conditions, be distributed in 500 parts of acetone, obtain alpha zirconium phosphate powder-acetone suspension liquid.Weigh the structure III type bifunctional polyetheramine that 50 parts of molecular weight are 600, be dispersed in 60 parts of acetone and obtain structure III type bifunctional polyetheramine-acetone dispersion liquor.By structure III type bifunctional polyetheramine-acetone dispersion liquor, be added drop-wise in 60 minutes in alpha zirconium phosphate powder-acetone suspension liquid.Drip rear 100 hertz of ultrasonic disperse 1h, magnetic particle stirs 12 hours, obtains alpha zirconium phosphate-structure III type bifunctional polyetheramine-acetone stripping liquid.Whizzer 5000 revs/min of rotating speeds carry out centrifugal treating to alpha zirconium phosphate-structure III type simple function group polyetheramine-acetone stripping liquid.Alpha zirconium phosphate-structure III type simple function group polyetheramine-acetone stripping liquid, after the process of 5000 revs/min, whizzer, is divided into a small amount of sediment bottom clarification upper liquid and centrifuge tube.By the upper liquid after centrifugal treating after 15000 revs/min of high speed centrifugation process, next sediment is the laminar alpha zirconium phosphate that molecular weight is the structure III type bifunctional polyetheramine stripping of 600.
Alpha zirconium phosphate 40 hertz of ultrasonic disperse of 15 parts of said structure III type bifunctional polyetheramine strippings are in 40 parts of acetone.85 parts of bisphenol-f type benzoxazine monomers are dissolved in 90 parts of acetone.Then by above-mentioned alpha zirconium phosphate/acetone dispersion liquor and benzoxazine monomer/acetone soln 40 hertz of ultrasonic disperse 30min.Adopt Rotary Evaporators, remove acetone under 50 and 100 DEG C of two temperature stage, and remove the air in benzoxazine monomer/alpha zirconium phosphate mixture.Being joined by bisphenol-f type benzoxazine monomer/alpha zirconium phosphate mixture adopts in the pretreated glass mold of releasing agent, in 100 DEG C of vacuum drying ovens after deaeration, mould and benzoxazine monomer/alpha zirconium phosphate mixture is transferred in temperature programming baking oven.140 DEG C solidify 4 hours, and 200 DEG C solidify 4 hours.In the process, bisphenol-f type benzoxazine monomer is open loop crosslinking reaction under alpha zirconium phosphate katalysis, forms bisphenol-f type benzoxazine/alpha zirconium phosphate nano composite material.After solidification process completes, naturally cooling, obtains the fire-retardant benzoxazine nano composite material of transparent type.
Embodiment 3
By the alpha zirconium phosphate powder that 5 parts of lamella diameters and thickness proportion are 20, under 40 hertz of ultrasound conditions, be distributed in 250 parts of acetone, obtain alpha zirconium phosphate powder-acetone suspension liquid.Weigh the structure I type simple function group polyetheramine that 16 parts of molecular weight are 1000, be dispersed in 50 parts of acetone and obtain structure I type simple function group polyetheramine-acetone dispersion liquor.By structure I type simple function group polyetheramine-acetone dispersion liquor, be added drop-wise in 25 minutes in alpha zirconium phosphate powder-acetone suspension liquid.Drip rear 40 hertz of ultrasonic disperse 1h, magnetic particle stirs 18 hours, obtains alpha zirconium phosphate-structure I type simple function group polyetheramine-acetone stripping liquid.Whizzer 10000 revs/min of rotating speeds carry out centrifugal treating to alpha zirconium phosphate-structure I type simple function group polyetheramine-acetone stripping liquid.Alpha zirconium phosphate-structure I type simple function group polyetheramine-acetone stripping liquid, after the process of 10000 revs/min, whizzer, is divided into a small amount of sediment bottom clarification upper liquid and centrifuge tube.By the upper liquid after above-mentioned centrifugal treating after 20000 revs/min of high speed centrifugation process, next sediment is the laminar alpha zirconium phosphate that molecular weight is the structure I type simple function group polyetheramine stripping of 1000.
Alpha zirconium phosphate 40 hertz of ultrasonic disperse of 10 parts of said structure I type simple function group polyetheramine strippings are in 40 parts of acetone.90 parts of bisphenol A-type benzoxazine monomers are dissolved in 90 parts of acetone.Then by above-mentioned alpha zirconium phosphate/acetone dispersion liquor and benzoxazine monomer/acetone soln 40 hertz of ultrasonic disperse 30min.Adopt Rotary Evaporators, remove acetone under 50 and 110 DEG C of two temperature stage, and remove the air in benzoxazine monomer/alpha zirconium phosphate mixture.Being joined by bisphenol A-type benzoxazine monomer/alpha zirconium phosphate mixture adopts in the pretreated glass mold of releasing agent, in 100 DEG C of vacuum drying ovens after deaeration, mould and benzoxazine monomer/alpha zirconium phosphate mixture is transferred in temperature programming baking oven.160 DEG C solidify 24 hours.In the process, bisphenol A-type benzoxazine monomer is open loop crosslinking reaction under alpha zirconium phosphate katalysis, forms bisphenol A-type benzoxazine colophony/alpha zirconium phosphate nano composite material.After solidification process completes, naturally cooling, obtains transparent type fire-retardant bisphenol A-type benzoxazine nano composite material.
Accompanying drawing 4 and accompanying drawing 5 are the heat release rate-time curve and the total burst size-time curve of carbon monoxide (CO) that obtain in resin material tapered calorimetric test after solidification described in embodiment 3 and comparative example 1 respectively.Comparing result shows, alpha zirconium phosphate effectively can reduce heat release rate and peak value in benzoxazine colophony combustion processes, can extend ignition time simultaneously, provide the more time for people escape in a fire.As long as CO is one of lethal reason in fire.With pure benzoxazine resin-phase ratio, in benzoxazine colophony/alpha zirconium phosphate nano composite material combustion processes, CO burst size significantly reduces.Accompanying drawing 6 is rear layer of charcoal (a) outside surface of resin material burning and (b) internal structure scanning electron microscope (SEM) photographs after solidification described in embodiment 3.As we can see from the figure, benzoxazine colophony/alpha zirconium phosphate nano composite material can form the layer of charcoal of outside surface densification, internal porous in combustion.This layer of charcoal effectively can play the effect intercepting Mass and heat transfer, and then reduces heat release rate, thus plays fire retardation.
Embodiment 4
By the alpha zirconium phosphate powder that 10 parts of lamella diameters and thickness proportion are 10, under 40 hertz of ultrasound conditions, be distributed in 300 parts of acetone, obtain alpha zirconium phosphate powder-acetone suspension liquid.Weigh the structure II type bifunctional polyetheramine that 25 parts of molecular weight are 200, be dispersed in 40 parts of acetone and obtain structure II type bifunctional polyetheramine-acetone dispersion liquor.By structure II type bifunctional polyetheramine-acetone dispersion liquor, be added drop-wise in 35 minutes in alpha zirconium phosphate powder-acetone suspension liquid.Drip rear 60 hertz of ultrasonic disperse 1.5h, magnetic particle stirs 16 hours, obtains alpha zirconium phosphate-structure II type bifunctional polyetheramine-acetone stripping liquid.Whizzer 10000 revs/min of rotating speeds carry out centrifugal treating to alpha zirconium phosphate-structure II type bifunctional polyetheramine-acetone stripping liquid.Alpha zirconium phosphate-structure II type bifunctional polyetheramine-acetone stripping liquid, after the process of 10000 revs/min, whizzer, is divided into a small amount of sediment bottom clarification upper liquid and centrifuge tube.By the upper liquid after above-mentioned centrifugal treating after 25000 revs/min of high speed centrifugation process, it is the laminar alpha zirconium phosphate that 200 structure II type bifunctional polyetheramines are peeled off that next sediment is molecular weight.
Alpha zirconium phosphate 40 hertz of ultrasonic disperse of 25 parts of said structure II type bifunctional polyetheramine strippings are in 100 parts of acetone.75 parts of phenolphthalein type benzoxazine monomers are dissolved in 50 parts of acetone.Then by above-mentioned alpha zirconium phosphate/acetone dispersion liquor and benzoxazine monomer/acetone soln 30 hertz of ultrasonic disperse 120min.Adopt Rotary Evaporators, remove acetone under 60 and 120 DEG C of two temperature stage, and remove the air in benzoxazine monomer/alpha zirconium phosphate mixture.Being joined by phenolphthalein type benzoxazine monomer/alpha zirconium phosphate mixture adopts in the pretreated glass mold of releasing agent, in 100 DEG C of vacuum drying ovens after deaeration, mould and benzoxazine monomer/alpha zirconium phosphate mixture is transferred in temperature programming baking oven.160 DEG C solidify 2 hours, and 200 DEG C solidify 4 hours.In the process, phenolphthalein type benzoxazine monomer is open loop crosslinking reaction under alpha zirconium phosphate katalysis, forms phenolphthalein type benzoxazine resin/alpha zirconium phosphate nano composite material.After solidification process completes, naturally cooling, obtains the fire-retardant benzoxazine nano composite material of transparent type.
Embodiment 5
By the alpha zirconium phosphate powder that 5 parts of lamella diameters and thickness proportion are 15, under 40 hertz of ultrasound conditions, be distributed in 200 parts of acetone, obtain alpha zirconium phosphate powder-acetone suspension liquid.Weigh the structure II type bifunctional polyetheramine that 10 parts of molecular weight are 2000, be dispersed in 20 parts of acetone and obtain structure II type bifunctional polyetheramine-acetone dispersion liquor.By structure II type bifunctional polyetheramine-acetone dispersion liquor, be added drop-wise in 25 minutes in alpha zirconium phosphate powder-acetone suspension liquid.Drip rear 40 hertz of ultrasonic disperse 1h, magnetic particle stirs 6 hours, obtains alpha zirconium phosphate-structure II type bifunctional polyetheramine-acetone stripping liquid.Whizzer 10000 revs/min of rotating speeds carry out centrifugal treating to alpha zirconium phosphate-structure II type bifunctional polyetheramine-acetone stripping liquid.Alpha zirconium phosphate-structure II type bifunctional polyetheramine-acetone stripping liquid, after the process of 10000 revs/min, whizzer, is divided into a small amount of sediment bottom clarification upper liquid and centrifuge tube.By the upper liquid after above-mentioned centrifugal treating after 25000 revs/min of high speed centrifugation process, next sediment is the laminar alpha zirconium phosphate that molecular weight is the structure II type bifunctional polyetheramine stripping of 2000.
Alpha zirconium phosphate 40 hertz of ultrasonic disperse of 1 part of said structure II type bifunctional polyetheramine stripping are in 5 parts of acetone.99 parts of polyethers amine type benzoxazine monomers are dissolved in 100 parts of acetone.Then by above-mentioned alpha zirconium phosphate/acetone dispersion liquor and benzoxazine monomer/acetone soln 20 hertz of ultrasonic disperse 100min.Adopt Rotary Evaporators, remove acetone under 50 and 110 DEG C of two temperature stage, and remove the air in benzoxazine monomer/alpha zirconium phosphate mixture.Being joined by polyethers amine type benzoxazine monomer/alpha zirconium phosphate mixture adopts in the pretreated glass mold of releasing agent, in 100 DEG C of vacuum drying ovens after deaeration, mould and benzoxazine monomer/alpha zirconium phosphate mixture is transferred in temperature programming baking oven.160 DEG C solidify 12 hours, and 180 DEG C solidify 4 hours.In the process, polyethers amine type benzoxazine monomer open loop crosslinking reaction under alpha zirconium phosphate katalysis, forms polyethers amine type benzoxazine colophony/alpha zirconium phosphate nano composite material.After solidification process completes, naturally cooling, obtains the fire-retardant benzoxazine nano composite material of transparent type.
Comparative example 1
After the 120 DEG C of meltings of 100 parts of bisphenol A-type benzoxazine monomers, join and adopt in the pretreated glass mold of releasing agent, in 120 DEG C of vacuum drying ovens after deaeration, mould and benzoxazine monomer are transferred in temperature programming baking oven.160 DEG C solidify 12 hours.In this solidification process, bisphenol A-type benzoxazine monomer open loop crosslinking reaction, forms bisphenol A-type benzoxazine colophony.After solidification process completes, naturally cooling, obtains pure benzoxazine material.
Application Example 1
The toughening flame-proof type epoxy resin of embodiment 4 being filled a prescription is applied to steel structure fireproofing coating.Embody rule implementation step is as follows, first will peel off state alpha zirconium phosphate completely and weigh in number ratio described in embodiment 4 in benzoxazine monomer, and carry out ultrasonic mixing by embodiment 4 step; Afterwards, by its high pressure painting on 200mm × 200mm × 3mm steel plate, coat-thickness 2mm, after the solidification of embodiment 4 condition, the flameproof effect of testing coating.Result shows, adopt comparative example 1 to fill a prescription prepared blank coating, without any flame retardant effect, the 1min steel plate back side just reaches 350 DEG C, and surface of steel plate generates without layer of charcoal.Reach 10min by the fill a prescription coating fire resistance period of preparation of embodiment 4, and at the foamed char of the fine and close consistent internal structure of Surface Creation outside surface, the highest thickness of layer of charcoal there is 13mm.There will not be in steel construction BENDING PROCESS by the coating of embodiment 4 formula preparation and come off and obvious crack, toughness is better.Wherein, flameproof effect adopts vertical combustion-large template die to intend combustion method test, and flameproof effect take fire resistance period as foundation, and the longer flameproof effect of fire resistance period is better.The critical temperature that steel construction loses static equilibrium stability is about 500 DEG C, loses its intensity of 1/3rd about 350 DEG C time, therefore will be designated as the fire resistance period of coating when the steel plate back temperature time reached required for 350 DEG C.Pliability test is tested on WDW-5 type microcomputer controlled electronic universal testing machine.
Claims (7)
1. the fire-retardant benzoxazine nano composite material of transparent type, is characterized in that, the fire-retardant benzoxazine nano composite material of described transparent type is peeled off state laminar alpha zirconium phosphate by 75 ~ 99 parts of benzoxazine colophonies and 1 ~ 25 part and formed;
Wherein, lamella diameter and the thickness proportion of peeling off state laminar alpha zirconium phosphate are 50 ~ 1000.
2. a preparation method for the fire-retardant benzoxazine nano composite material of transparent type as claimed in claim 1, it is characterized in that, the method comprises the following steps:
(1) 1 ~ 25 part is peeled off state laminar alpha zirconium phosphate ultrasonic disperse in 5 ~ 200 parts of acetone;
(2) by 75 ~ 99 parts of benzoxazine monomer stirring and dissolving in 50 ~ 100 parts of acetone;
(3) slowly joined by the solution that step (2) obtains in the solution that step (1) obtains, ultrasonic disperse 30 ~ 120min obtains the mixture containing benzoxazine monomer/alpha zirconium phosphate afterwards;
(4) adopt Rotary Evaporators, the acetone contained in the mixture of benzoxazine monomer/alpha zirconium phosphate that 50 ~ 120 DEG C of gradient increased temperature removing steps (3) obtain, and remove air wherein;
(5) material that step (4) obtains is joined adopt in the pretreated glass mold of releasing agent, 100 ~ 130 DEG C of vacuum defoamations;
(6) material after deaeration to be transferred to together with mould in temperature programming baking oven 140 ~ 160 DEG C of solidifications 2 ~ 24 hours, 180 ~ 200 DEG C of solidifications 0 ~ 4 hour; In the process, benzoxazine monomer is open loop crosslinking reaction under the katalysis of stripping state laminar alpha zirconium phosphate, finally forms the transparent flame-retarding type nano composite material of benzoxazine colophony/alpha zirconium phosphate composition; After solidification process completes, after naturally cooling, obtain the fire-retardant benzoxazine nano composite material of described transparent type.
3. the preparation method of the fire-retardant benzoxazine nano composite material of transparent type according to claim 2, is characterized in that, ultrasonic described in step (1) and step (3), its frequency be 20 ?40 hertz.
4. the preparation method of the fire-retardant benzoxazine nano composite material of the transparent type according to Claims 2 or 3, it is characterized in that, the benzoxazine monomer in step (2) is the bisphenol-f type benzoxazine monomer (one of structure a), in bisphenol A-type benzoxazine monomer (structure b), phenolphthalein type benzoxazine monomer (structure c) or thiodiphenol type benzoxazine monomer (structure d);
5. the preparation method of the fire-retardant benzoxazine nano composite material of the transparent type according to Claims 2 or 3, it is characterized in that, the preparation method peeling off state laminar alpha zirconium phosphate in described method comprises the steps:
(1) by 5 ~ 15 parts of lamella diameters and thickness proportion be 5 ~ 20 alpha zirconium phosphate powder, under 40 ~ 100 hertz of ultrasound conditions, be distributed in 200 ~ 500 parts of acetone;
(2) weigh 10-50 part simple function group or bifunctional polyetheramine, be dispersed in 20-60 part acetone and obtain polyetheramine-acetone dispersion liquor;
(3) by the polyetheramine-acetone dispersion liquor of step (2), be added drop-wise in the solution that step (1) obtains within the scope of 25-60 minutes; 40 ~ 100 hertz of ultrasonic disperse 1 ~ 3h after dripping, magnetic particle stirs 6 ~ 24 hours, obtains alpha zirconium phosphate-polyetheramine-acetone stripping liquid;
(4) alpha zirconium phosphate-polyetheramine-acetone stripping liquid of supercentrifuge to step (3) is adopted to carry out centrifugal treating;
(5) by the upper liquid after step (4) centrifugal treating after 15000 ~ 25000 revs/min of high speed centrifugation process, next sediment is the stripping state laminar alpha zirconium phosphate that lamella diameter and thickness proportion are 50 ~ 1000.
6. the preparation method of the fire-retardant benzoxazine nano composite material of transparent type according to claim 5, it is characterized in that, peel off state layer Zhuan α ?the simple function group described in step (2) of preparation method of zirconium phosphate or bifunctional polyetheramine be one below in structure (I), structure (II) or structure (III):
Wherein, in structure (I), x/y=0.1 ~ 9, molecular weight is 600 ~ 2000; In structure (II), x=2 ~ 35, molecular weight is 200 ~ 2000; In structure (III), x+z=1 ~ 6, y=2 ~ 40, molecular weight is 200 ~ 2000.
7. the preparation method of the fire-retardant benzoxazine nano composite material of the transparent type according to claim 5 or 6, it is characterized in that, peel off state layer Zhuan α ?the centrifugation step speed described in step (4) of preparation method of zirconium phosphate be 5000-10000 rev/min.
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| CN107474208B (en) * | 2017-08-01 | 2019-10-22 | 四川天策聚材科技有限公司 | A kind of multi-functional benzoxazine composite material and preparation method |
| CN112980135A (en) * | 2021-02-24 | 2021-06-18 | 西南石油大学 | Flame-retardant and toughened benzoxazine/bio-based phosphide composite material and preparation method thereof |
| CN112980135B (en) * | 2021-02-24 | 2022-06-10 | 西南石油大学 | Flame-retardant and toughened benzoxazine/bio-based phosphide composite material and preparation method thereof |
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