CN109749383A - A kind of method of composite flame-retardant agent modified unsaturated polyester - Google Patents
A kind of method of composite flame-retardant agent modified unsaturated polyester Download PDFInfo
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- CN109749383A CN109749383A CN201711118764.0A CN201711118764A CN109749383A CN 109749383 A CN109749383 A CN 109749383A CN 201711118764 A CN201711118764 A CN 201711118764A CN 109749383 A CN109749383 A CN 109749383A
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- unsaturated polyester
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- ammonium polyphosphate
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- 229920006305 unsaturated polyester Polymers 0.000 title claims abstract description 167
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000012757 flame retardant agent Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 45
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 45
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 45
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 31
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- 239000010452 phosphate Substances 0.000 claims abstract description 16
- 238000013019 agitation Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims description 84
- 238000001035 drying Methods 0.000 claims description 13
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 11
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 11
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 11
- 238000007711 solidification Methods 0.000 claims description 10
- 230000008023 solidification Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 20
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 79
- 230000000052 comparative effect Effects 0.000 description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 36
- 239000001301 oxygen Substances 0.000 description 36
- 229910052760 oxygen Inorganic materials 0.000 description 36
- 239000000463 material Substances 0.000 description 25
- DBLHYLDWZSNRBI-UHFFFAOYSA-N N=NC=NN.N=NC=NN.P(=O)(O)(O)O Chemical compound N=NC=NN.N=NC=NN.P(=O)(O)(O)O DBLHYLDWZSNRBI-UHFFFAOYSA-N 0.000 description 16
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 229920000728 polyester Polymers 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000003610 charcoal Substances 0.000 description 9
- 239000000571 coke Substances 0.000 description 9
- 235000003642 hunger Nutrition 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CAAULPUQFIIOTL-UHFFFAOYSA-L methyl phosphate(2-) Chemical compound COP([O-])([O-])=O CAAULPUQFIIOTL-UHFFFAOYSA-L 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001594303 Lepidoscia polymeres Species 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- -1 ethoxy cyanurate Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of method of composite flame-retardant agent modified unsaturated polyester, mainly includes the following steps: that (1) ammonium polyphosphate is uniformly mixed under agitation with unsaturated polyester (UP), then obtain ammonium polyphosphate modifying after initiator solidifies；(2) unsaturated polyester (UP) is modified to get modified unsaturated poly- to a kind of composite flame-proof through montmorillonite, zinc borate, two formicester of methyl acid phosphate, ammonium polyphosphate modifying and initiator respectively.Compared with prior art, composite flame-retardant agent of the invention and unsaturated polyester (UP) have good compatibility, can greatly improve ammonium polyphosphate dispersibility in the base and interface interaction, have significant cooperative flame retardant effect.
Description
Technical field
The present invention relates to flame retarded polymeric material technical fields, and in particular to a kind of composite flame-retardant agent modified unsaturated polyester
Method.
Background technique
Unsaturated polyester resin is a kind of linear polymer with ester bond and unsaturated double-bond, usually by two
What first carboxylic acid and dihydric alcohol were synthesized by polycondensation reaction.Unsaturated polyester (UP) aggressiveness, which is generally dissolved in styrene, forms solution,
The thermosetting resin patent CN102838779A for being formed by curing three-dimensional-structure through initiator initiation when use discloses a kind of compound
Type expanding fire retardant modified heat convertible resin.The mixed solution of phosphorus oxychloride and dioxane is added to expansible graphite and two
Six ring of oxygen is uniformly mixed, and polyalcohol and catalyst is added, obtains a kind of phosphorous organic expander type fire retardant, but in the technique mistake
Fire retardant compatibility is bad in journey.Patent CN105384387A discloses a kind of composite flame-retardant agent and its preparation method and application,
But fire retardant additive amount is big in the technical process.Unsaturated polyester resin is that thermosetting plastics purposes is most widely a kind of,
Since with easy to process, raw material, the excellent performances such as cheap, waterproof and oilproof, resistant to chemical etching are widely used in communications and transportation for it
Industry (vehicle internal/external and other structures component, the various helmets, traffic sign etc.), urban duct facility (pipeline, cabinet,
Switch etc.), building construction (door and window, dining table seat, ornament materials, plate, fire-fighting equipment etc.), power industry (small members, electricity
Device switch, cover, motor blade etc.) and the fields such as medical, building materials, craftwork, dress ornament, sport, light industry device village (referring to document
Baljinder K.Kandola, John R.Ebdon, Piyanuch Luangtriratana, Latha
Krishnan.Polymer Degradation and Stability, 2016,127:56-64.).Therefore, it is related to unsaturated poly-
The product of ester resin plays irreplaceable role in various fields of recent life.
Ammonium polyphosphate is a kind of aggretion type inorganic phosphate esters fire retardant, and general formula is (NH4)n+2PnO3n+1, theoretical phosphorus,
Nitrogen content is respectively 31.92wt% and 14.44wt%, is widely used in the fire-retardant of the polymer materials such as plastics, fiber, rubber.
When the polymer material containing ammonium polyphosphate is subjected to fire, ammonium polyphosphate will resolve into polyphosphoric acid and ammonia first, then more phosphorus
Acid is reacted with hydroxyl or other synergist groups such as ethoxy cyanurate or ring urea formaldehyde resin, forms unstable phosphoric acid
Ester.
It in phosphate dehydration, will carbonize comprising formed in the surface of polymer material and resist heat source
Carbon foam.In addition, viscous molten layer or watch crystal can also be obtained on polymer surfaces in addition to forming carbon foam, protect
Polymer material is protected from heat and oxygen.In flame retardant thermoset resins such as unsaturated polyester (UP) and epoxy resin, ammonium polyphosphate can
To be used alone.However, ammonium polyphosphate has very strong hydrophily and a degree of layering, the layering in use process can drop
The anti-flammability of low material.In addition, the poor compatibility of ammonium polyphosphate and polymer, this will damage the mechanical performance of material.In order to gram
The shortcomings that taking above-mentioned ammonium polyphosphate, the present invention have carried out corresponding modification to ammonium polyphosphate.
Montmorillonite layer has very strong fixed function to unsaturated polyester (UP) molecule, and the barrier action of montmorillonite layer can
To prevent the transmission of heat and combustible volatile, promote polymer at charcoal, simultaneously because cannot fire completely after polymer matrix is heated
It burns and is converted into more charcoal residues.Anti-flammability mostlys come from montmorillonite layer to the barrier action and burning of interlayer macromolecular
The formed layer of charcoal in surface it is heat-insulated, every matter act on (referring to document Goodarzi V, Monemian S A, Angaji M T, et
Al.Journal of applied polymer science, 2008,110 (5): 2971-2979.).
The compactness of layer of charcoal can be enhanced in zinc borate, this will easily discharge water at relatively high temperatures and form boric acid, to promote
The formation of pyrolytic layer in unsaturated polyester (UP).Zinc borate is a kind of multifunctional fire retardant, have it is fire-retardant, at charcoal, suppression cigarette, suppression glow
With prevent from generating the multiple functions such as molten drop (referring to document Braun U, Schartel B, Fichera M A, et al.Polymer
Degradation and Stability, 2007,92 (8): 1528-1545.).It can be melted at a higher temperature in solid phase
Change, and form vitreum coating, isolation air effect is played on the surface of blocked polymer.
Methyl-phosphoric acid dimethyl ester, is a kind of low-viscosity liquid additive flame retardant being halogen-free, its phosphorus content is up to
25%, excellent flame retardancy is (referring to document Feng F, Qian L.Polymer Composites, 2014,35 (2): 301-
309.).In addition to excellent fireproof performance, relative to other fire retardants, there are also lower temperature resistance, plasticity, UV stable, drainings
Property, self-extinguishment the advantages that, the characteristics of especially it can be used for the coating article of transparent or light graceful color, this is other resistances
The characteristic that combustion agent does not have.
Summary of the invention
For the flame retardant property for improving unsaturated polyester (UP), the invention proposes a kind of composite flame-retardant agent modified unsaturated polyesters
Method, specifically includes the following steps:
(1) ammonium polyphosphate is uniformly mixed under agitation with unsaturated polyester (UP) in mass ratio 1: 1；
(2) initiator is added into step (1) resulting solution under agitation, obtains solution A；
(3) it is put into drying box after solution A being infused film, pulverizes and sieves after solidification demoulding, obtains ammonium polyphosphate modifying；
(4) montmorillonite is mixed under agitation with unsaturated polyester (UP), both control mass ratio is (1~9): 68, temperature
Degree is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution B after mixing；
(5) zinc borate is mixed under agitation with step (4) resulting solution B, controls zinc borate dosage and step
(4) mass ratio of montmorillonite is 2 in: (1~9), temperature are 20 DEG C~30 DEG C, and mixing time is 10min~20min, and mixing is equal
Solution C is obtained after even；
(6) two formicester of methyl acid phosphate is added in solution C under agitation, controls two formicester of methyl acid phosphate and step
(5) mass ratio of the zinc borate in is 5: 1, and temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, after mixing
Obtain solution D；
(7) step (3) resulting ammonium polyphosphate modifying is added in solution D under agitation, controls modified polyphosphoric acid
The mass ratio of two formicester of methyl acid phosphate is (9~17) in ammonium and step (6): 10, temperature is 20 DEG C~30 DEG C, and mixing time is
10min~20min obtains solution after mixing；
(8) initiator will be added in step (7) resulting solution, obtains solution E, be put into drying box after infusing film, exist respectively
At 80 DEG C, 110 DEG C solidify 1h and 3h, cooling and demolding to get arrive a kind of modified unsaturated polyester.
In the present invention, the initiator is benzoyl peroxide.
In the present invention, the granularity of the ammonium polyphosphate modifying is 300~400 mesh.
In the present invention, the mass ratio of the unsaturated polyester (UP) and composite flame-retardant agent is (70~100): 30.
Compared with prior art, the beneficial effect that the present invention obtains is: (1) dispersed after the modified processing of ammonium polyphosphate
It is good, be not easy to be layered, and greatly improve with the compatibility of high molecular material, can greatly improve unsaturated polyester (UP) flame retardant property and
Mechanical performance；(2) montmorillonite layer has very strong fixed function to unsaturated polyester (UP) molecule, and the barrier of montmorillonite layer is made
With the transmission that can prevent heat and combustible volatile, promote polymer at charcoal；(3) phosphorous organic expander type fire retardant is with chemistry
Bonded mode coats, and fine and close protective layer can be formed in heated and burning, so that it is excellent to assign modified unsaturated polyester
Heat resistance and anti-flammability；(4) addition of zinc borate can be improved the fire-retardant and smoke suppressing of material.Therefore, prepared to change
Property unsaturated polyester (UP) have excellent flame retardant property.
Detailed description of the invention
Fig. 1 is the work flow diagram of modified unsaturated polyester of the present invention；
Fig. 2 be present example 1,2,3,4,5,6,7,8 provide modified unsaturated polyester and comparative example 1 provide it is pure not
The limit oxygen index column comparison diagram of saturated polyester solidfied material；
Fig. 3 is the modified unsaturated polyester that present example 1,3 and 5 provides and the pure unsaturated polyester (UP) that comparative example 1 provides
TG (a) of the solidfied material in nitrogen atmosphere and DTG (b) curve；
Fig. 4 is the modified unsaturated polyester that present example 1,3 and 5 provides and the pure unsaturated polyester (UP) that comparative example 1 provides
TG (a) of the solidfied material in air atmosphere and DTG (b) curve；
Fig. 5 is the modified unsaturated polyester that present example 1,3 and 5 provides and the pure unsaturated polyester (UP) that comparative example 1 provides
After the oxygen index (OI) experiment of solidfied material, the stereoscan photograph of carbon residue outer surface；
Fig. 6 is the modified unsaturated polyester that present example 1 provides and the pure Cured up resin that comparative example 1 provides
Average heat release rate and total heat releasing curve diagram.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Except there is a special instruction, the various reagents used in the present invention, raw material be can commodity commercially or
Person can the product as made from well known method.
With reference to the accompanying drawings and examples, the technical solution used to invention is further elaborated.
Comparative example 1
1, the preparation of composite flame-retardant agent modified unsaturated polyester
It is 20 DEG C~30 DEG C that the initiator benzoyl peroxide of 4g, which is added to mixing temperature in the unsaturated polyester (UP) of 196g,
Mixing time is 10min~20min, obtains solution E；
It is put into drying box after solution E is infused film, for the first time with 80 DEG C of dry 1 hours；Second with 110 DEG C of solidifications 3
Hour, demoulding is taken out to get the pure sample of unsaturated polyester (UP) is arrived after being cooled to room temperature.Its TG (a) and DTG in nitrogen atmosphere
(b) after curve, the TG (a) in air atmosphere and DTG (b) curve, oxygen index (OI) experiment, the scanning electron microscope of carbon residue outer surface is shone
Piece, the result of viscosity test, heat release rate and total heat releasing curve diagram, limit oxygen index are respectively referring to attached drawing 1,2,3,4,5
With 6.
Referring to attached drawing 1, it is the work flow diagram of modified unsaturated polyester of the present invention.
Referring to attached drawing 2, it is the oxygen index (OI) test result figure of pure Cured up resin.It can be seen that pure unsaturation
The oxygen index value of polyester is 18.9%, this shows that the anti-flammability of pure unsaturated polyester (UP) is poor.
Referring to attached drawing 3, it is TG (a) of the comparative example 1 in nitrogen atmosphere and DTG (b) curve.It can be seen that example 1 exists
Degradation process in nitrogen atmosphere is divided into two Main Stages, and pure unsaturated polyester (UP) starts to degrade after 200 DEG C, the first stage
It is corresponding with dehydration within the temperature range of 210-320 DEG C.However, mass loss is only about 8wt%, due to the step
Mass loss very little, without apparent peak value establish on DTG curve.As the temperature rises, quick loss of weight another
Stage is within the temperature range of 320-450 DEG C.The stage main weight loss is attributed to the disconnected of unsaturated polyester cross-linking structure
Chain, the weight of residual coke is smaller after 500 DEG C.
Referring to attached drawing 4, it is TG (a) of the comparative example 1 in air atmosphere and DTG (b) curve.With phase under nitrogen atmosphere
Than the TG curve of pure unsaturated polyester (UP) is presented in entire degradation process due to the further decomposition of the charcoal of formation in air
Three phases.Therefore, from DTG curve, occurs another mass loss wave within the temperature range of 450-550 DEG C.
Referring to attached drawing 5, it is the sem image of pure Cured up resin charring layer after oxygen index (OI) test.It can see
Out there are many wide about 100 μm of netted apertures and many irregular micro- in the surface of pure Cured up resin carbonaceous layer
See aperture.This unsound carbonaceous layer not can effectively prevent heat and penetrate the polymer being heated from flame zone and pass to substrate.
Referring to attached drawing 6, it be the modified unsaturated polyester that comparative example 1 and example 1 of the present invention provide heat release rate and
Total heat releasing curve diagram.It can be found that composite flame-retardant agent addition modified unsaturated polyester is significantly reduced peak heat release rate.
The peak heat release rate that comparative example 1 obtains is 581kW/m2.Comparative example 1 rapidly and efficiently produces the spike of heat release rate
The peak and.On the other hand, the heat release rate peak value of comparative example 1 is higher and relatively narrow.
Embodiment 1
1, the preparation of composite flame-retardant agent modified unsaturated polyester
The montmorillonite of 2g being added in the unsaturated polyester (UP) of 136g, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C,
Mixing time is 10min~20min, obtains solution B；
It is 1: 2 by montmorillonite and zinc borate mass ratio, the zinc borate of 4g is added in above-mentioned solution A, is stirred
Even, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution C；
It is 1: 5 by zinc borate and methyl acid phosphate diformazan rouge mass ratio, two formicester of methyl acid phosphate of 20g is added to above-mentioned molten
It in liquid C, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution D；
It is 17: 10 by ammonium polyphosphate modifying and methyl acid phosphate diformazan rouge mass ratio, the ammonium polyphosphate modifying of 34g is added to
It in above-mentioned solution D, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, is obtained molten
Liquid；The benzoyl peroxide initiator that 4g is added in solution again obtains solution E after mixing evenly.
It is put into drying box after solution E is infused film, for the first time with 80 DEG C of dry 1 hours；Second with 110 DEG C of solidifications 3
Hour, it demoulds and takes out after being cooled to room temperature, obtain modified unsaturated polyester.Solidify the typical performance of unsaturated polyester (UP) respectively referring to
Attached drawing 1,2,3,4,5 and 6.
TGA data of the table 1 under air and nitrogen atmosphere
Referring to attached drawing 1, it is the work flow diagram of modified unsaturated polyester of the present invention.
Referring to attached drawing 2, it is composite flame-proof modified unsaturated polyester provided by the invention and the pure insatiable hunger that comparative example 1 provides
With the oxygen index (OI) test result figure of polyester.It can be seen that the oxygen index (OI) of example 1 is 31.25, oxygen index (OI) highest.
Referring to attached drawing 3, it is present example, 1,3, the 5 composite flame-proof modified unsaturated polyester material provided and comparison
TG (a) and DTG (b) curve of the pure unsaturated polyester (UP) that example 1 provides in nitrogen atmosphere, typical data is referring to table 1.It can send out
The thermal oxide decomposable process and comparative example 1 of real example 1 have the similar stage, however, by the way that composite flame-retardant agent is modified insatiable hunger
And polyester, decompose significant change.With T of the comparative example 1 at 308 DEG C0.1Compare, example 1 is at a lower temperature than comparative example 1
It is early to decompose.It is worth noting that example 1 has minimum decomposition temperature compared with other samples.The T of example 1maxLower than comparative example
1, the composite flame-retardant agent of ammonium polyphosphate modifying can reduce biggest quality loss late, show that example 1 is decomposed slowly than comparative example 1.With
The thermal stability of the increase of montmorillonite amount, modified unsaturated polyester is high.The significant increase of residue at 350 DEG C than 500 DEG C.It is real
Coke yield of the example 1 at 800 DEG C is 31.3wt%, much higher than the 1.7wt% of ratio 1.The coke of formation will limit combustible gas
The release of body and the thermal conductivity for reducing incendiary material, therefore the combustibility of material can be delayed.
Referring to attached drawing 4, it is the composite flame-proof modified unsaturated polyester material and comparative example 1 that present example 1,3,5 provides
TG (a) and DTG (b) curve of the pure unsaturated polyester (UP) provided in air atmosphere, typical data is referring to table 1.It can be found that
When example 1 and comparative example 1 are assessed in air atmosphere, degradation behavior is different from the degradation behavior in nitrogen.It is obvious that
Replace the thermal degradation mechanism of non-oxidizing atmosphere promotion sample by air.The heat drop of the modified unsaturated polyester (UP) of composite flame-retardant agent
Solution preocess has similar three phases with comparative example 1.However, by by different amounts of zinc borate, montmorillonite, ammonium polyphosphate modifying
Carry out modified unsaturated polyester and also reduces degradative pathway.Compared with comparative example 1, the T of example0.1Temperature in each case is all
It is lower.The T of example 10.1Minimum 171 DEG C.
Referring to attached drawing 5, it is the composite flame-proof modified unsaturated polyester material and comparative example 1 that present example 1,3,5 provides
The sem image of the pure unsaturated polyester (UP) provided charring layer after oxygen index (OI) test.Can clearly find, this four samples it
Between there are great differences.As shown in figure (a), it can be observed that the structure of relative loose and multiple depth crackle in comparative example 1, and
And there are many macropores for distribution on the surface.For the coke residue figure (b, d) of example 1 and example 5, form more swelling and cause
It is close.The honeycomb charcoal of example 1 and example 5 can the significant quality and energy transmission reduced in combustion process, thus to be following
Material provides better anti-flammability, and improves the anti-flammability of unsaturated polyester (UP).
Referring to attached drawing 6, it be the modified unsaturated polyester that comparative example 1 and example 1 of the present invention provide heat release rate and
Total heat releasing curve diagram.It can be found that composite flame-retardant agent addition modified unsaturated polyester is significantly reduced peak heat release rate.
The peak heat release rate that comparative example 1 obtains is 581kW/m2, and it is 280kW/m that example 1, which obtains lower peak heat release rate,2.It is right
Ratio 1 rapidly and efficiently produces spike and the peak of heat release rate.On the other hand, modified not containing composite flame-retardant agent
The heat release rate peak value of saturated polyester example 1 is lower and wider, and burning time also extends.
Embodiment 2
1, the preparation of composite flame-retardant agent modified unsaturated polyester
The montmorillonite of 10g is added in the unsaturated polyester (UP) of 136g, is uniformly mixed, mixing temperature is 20 DEG C~30
DEG C, mixing time is 10min~20min, obtains solution B；
It is 1: 2 by montmorillonite and methyl acid phosphate diformazan rouge mass ratio, two formicester of methyl acid phosphate of 20g is added to above-mentioned molten
It in liquid B, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution D；
It is 3: 2 by ammonium polyphosphate modifying and methyl acid phosphate diformazan rouge mass ratio, the ammonium polyphosphate modifying of 30g is added to
It states in solution D, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution；
The benzoyl peroxide initiator that 4g is added in solution again obtains solution E after mixing evenly.
It is put into drying box after solution E is infused film, for the first time with 80 DEG C of dry 1 hours；Second with 110 DEG C of solidifications 3
Hour, it demoulds and takes out after being cooled to room temperature, obtain modified unsaturated polyester.Solidify the typical performance of unsaturated polyester (UP) respectively referring to
Attached drawing 2.
Referring to attached drawing 2, it is composite flame-proof modified unsaturated polyester provided by the invention and the pure insatiable hunger that comparative example 1 provides
With the oxygen index (OI) test result figure of polyester.It can be seen that the oxygen index (OI) of example 2 is 30.12, with comparative example after being added to fire retardant
1 oxygen index (OI) is compared for 18.9 and is significantly improved.
Embodiment 3
1, the preparation of composite flame-retardant agent modified unsaturated polyester
The montmorillonite of 6g being added in the unsaturated polyester (UP) of 136g, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C,
Mixing time is 10min~20min, obtains solution B；
It is 3: 10 by montmorillonite and methyl acid phosphate diformazan rouge mass ratio, two formicester of methyl acid phosphate of 20g is added to above-mentioned
It in solution B, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution D；
It is 17: 10 by ammonium polyphosphate modifying and methyl acid phosphate diformazan rouge mass ratio, the ammonium polyphosphate modifying of 34g is added to
It in above-mentioned solution D, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, is obtained molten
Liquid；The benzoyl peroxide initiator that 4g is added in solution again obtains solution E after mixing evenly.
It is put into drying box after solution E is infused film, for the first time with 80 DEG C of dry 1 hours；Second with 110 DEG C of solidifications 3
Hour, it demoulds and takes out after being cooled to room temperature, obtain modified unsaturated polyester.Solidify the typical performance of unsaturated polyester (UP) respectively referring to
Attached drawing 2,3,4 and 5.
Referring to attached drawing 2, it is composite flame-proof modified unsaturated polyester provided by the invention and the pure insatiable hunger that comparative example 1 provides
With the oxygen index (OI) test result figure of polyester.It can be seen that the oxygen index (OI) of example 3 is 30.49, the oxygen index (OI) with comparative example 1 is 18.9
Compared to being significantly improved.
Referring to attached drawing 3, it is present example, 1,3, the 5 composite flame-proof modified unsaturated polyester material provided and comparison
TG (a) and DTG (b) curve of the pure unsaturated polyester (UP) that example 1 provides in nitrogen atmosphere, typical data is referring to table 1.Example 3
TmaxThe composite flame-retardant agent of slightly below comparative example 1, ammonium polyphosphate modifying can reduce biggest quality loss late, show that example 3 compares
Ratio 1 is decomposed slowly.With the increase of montmorillonite amount, the thermal stability of modified unsaturated polyester is high.At 350 DEG C than 500 DEG C
The significant increase of residue.Coke yield of the example 3 at 800 DEG C is 35wt%, much higher than the 1.7wt% of ratio 1.
Referring to attached drawing 4, it is the composite flame-proof modified unsaturated polyester material and comparative example that present example 1,3,5 provides
TG (a) and DTG (b) curve of the 1 pure unsaturated polyester (UP) provided in air atmosphere, typical data is referring to table 1.It can be found that
When example 3 and comparative example 1 are assessed in air atmosphere, compared with comparative example 1, the T of example 30.1Temperature in each case
It spends all lower.The T of example 30.1It is 173 DEG C.
Referring to attached drawing 5, it is the composite flame-proof modified unsaturated polyester material and comparative example 1 that present example 1,3,5 provides
The sem image of the pure unsaturated polyester (UP) provided charring layer after oxygen index (OI) test.Can clearly find, this four samples it
Between there are great differences.For the coke residue figure (c) of example 3, the structure of relative smooth and pyknosis is observed, due to by
The reaction of formation and the montmorillonite of the phosphoric acid that the decomposition reaction of methyl-phosphoric acid dimethyl ester generates, cheating engaging layer is to unsaturated polyester (UP) point
Son has very strong fixed effect.
Embodiment 4
1, the preparation of composite flame-retardant agent modified unsaturated polyester
The montmorillonite of 14g is added in the unsaturated polyester (UP) of 136g, is uniformly mixed, mixing temperature is 20 DEG C~30
DEG C, mixing time is 10min~20min, obtains solution B；
It is 7: 10 by montmorillonite and methyl acid phosphate diformazan rouge mass ratio, two formicester of methyl acid phosphate of 20g is added to above-mentioned
It in solution B, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution D；
It is 13: 10 by ammonium polyphosphate modifying and methyl acid phosphate diformazan rouge mass ratio, the ammonium polyphosphate modifying of 26g is added to
It in above-mentioned solution D, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, is obtained molten
Liquid；The benzoyl peroxide initiator that 4g is added in solution again obtains solution E after mixing evenly.
It is put into drying box after solution E is infused film, for the first time with 80 DEG C of dry 1h；For the second time with 110 DEG C of dry 3h, it is cooled to
It demoulds and takes out after room temperature, obtain modified unsaturated polyester.Solidify the typical performance of unsaturated polyester (UP) respectively referring to attached drawing 2.
Referring to attached drawing 2, it is composite flame-proof modified unsaturated polyester provided by the invention and the pure insatiable hunger that comparative example 1 provides
With the oxygen index (OI) test result figure of polyester.It can be seen that the oxygen index (OI) of example 4 is 27.4, the oxygen index (OI) of example 4 is than comparative example 1
It is low.
Embodiment 5
1, the preparation of composite flame-retardant agent modified unsaturated polyester
The montmorillonite of 6g being added in the unsaturated polyester (UP) of 136g, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C,
Mixing time is 10min~20min, obtains solution B；
It is 3: 2 by montmorillonite and zinc borate mass ratio, the zinc borate of 4g is added in above-mentioned solution B, is stirred
Even, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution C；
It is 1: 5 by zinc borate and methyl acid phosphate diformazan rouge mass ratio, two formicester of methyl acid phosphate of 20g is added to above-mentioned molten
It in liquid C, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution D；
It is 3: 2 by ammonium polyphosphate modifying and methyl acid phosphate diformazan rouge mass ratio, the ammonium polyphosphate modifying of 30g is added to
It states in solution D, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution；
The benzoyl peroxide initiator that 4g is added in solution again obtains solution E after mixing evenly.
It is put into drying box after solution E is infused film, for the first time with 80 DEG C of dry 1 hours；Second with 110 DEG C of solidifications 3
Hour, it demoulds and takes out after being cooled to room temperature, obtain modified unsaturated polyester.Solidify the typical performance of unsaturated polyester (UP) respectively referring to
Attached drawing 2,3,4 and 5.
Referring to attached drawing 2, it is composite flame-proof modified unsaturated polyester provided by the invention and the pure insatiable hunger that comparative example 1 provides
With the oxygen index (OI) test result figure of polyester.It can be seen that from example 5 to example 8, with the reduction and illiteracy of ammonium polyphosphate modifying amount
The increase of de- soil amount, oxygen index value reduce, and the efficiency for reflecting ammonium polyphosphate modifying fire retardant is higher than montmorillonite.With montmorillonite
Increase, oxygen index (OI) is gradually reduced.The dispersion of montmorillonite and the property of aggregation difference make composite material reach layered structure.Work as addition
It is flammable therefore improve that as was expected when excessive montmorillonite.
Referring to attached drawing 3, it is present example, 1,3, the 5 composite flame-proof modified unsaturated polyester material provided and comparison
TG (a) and DTG (b) curve of the pure unsaturated polyester (UP) that example 1 provides in nitrogen atmosphere, typical data is referring to table 1.It can send out
The thermal oxide decomposable process and comparative example 1 of real example 5 have the similar stage, however the residue at 350 DEG C than 500 DEG C is aobvious
Increase.Coke yield of the example 5 at 800 DEG C is 31.6wt%, much higher than the 1.7wt% of ratio 1.The coke of formation will limit
The release of fuel gas processed and the thermal conductivity for reducing incendiary material, therefore the combustibility of material can be delayed.
Referring to attached drawing 4, it is the composite flame-proof modified unsaturated polyester material and comparative example 1 that present example 1,3,5 provides
TG (a) and DTG (b) curve of the pure unsaturated polyester (UP) provided in air atmosphere, typical data is referring to table 1.It can be found that
When example 5 and comparative example 1 are assessed in air atmosphere, degradation behavior is different from the degradation behavior in nitrogen.
Referring to attached drawing 5, it is the composite flame-proof modified unsaturated polyester material and comparative example 1 that present example 1,3,5 provides
The sem image of the pure unsaturated polyester (UP) provided charring layer after oxygen index (OI) test.For the coke residue figure (d) of example 5,
Form more swelling and densification.The honeycomb charcoal of example 5 can it is significant reduce combustion process in quality and energy transmission, thus
Better anti-flammability is provided for following material, and improves the anti-flammability of unsaturated polyester (UP).
Example 6
1, the preparation of composite flame-retardant agent modified unsaturated polyester
The montmorillonite of 10g is added in the unsaturated polyester (UP) of 136g, is uniformly mixed, mixing temperature is 20 DEG C~30
DEG C, mixing time is 10min~20min, obtains solution B；
It is 5: 2 by montmorillonite and zinc borate mass ratio, the zinc borate of 4g is added in above-mentioned solution B, is stirred
Even, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution C；
It is 1: 5 by zinc borate and methyl acid phosphate diformazan rouge mass ratio, two formicester of methyl acid phosphate of 20g is added to above-mentioned molten
It in liquid C, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution D；
It is 13: 10 by ammonium polyphosphate modifying and methyl acid phosphate diformazan rouge mass ratio, the ammonium polyphosphate modifying of 26g is added to
It in above-mentioned solution D, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, is obtained molten
Liquid；The benzoyl peroxide initiator that 4g is added in solution again obtains solution E after mixing evenly.
It is put into drying box after solution E is infused film, for the first time with 80 DEG C of dry 1 hours；Second with 110 DEG C of solidifications 3
Hour, it demoulds and takes out after being cooled to room temperature, obtain modified unsaturated polyester.Solidify the typical performance of unsaturated polyester (UP) respectively referring to
Attached drawing 2.
Referring to attached drawing 2, it is composite flame-proof modified unsaturated polyester provided by the invention and the pure insatiable hunger that comparative example 1 provides
With the oxygen index (OI) test result figure of polyester.The oxygen index (OI) of example 6 is 29.41.
Embodiment 7
1, the preparation of composite flame-retardant agent modified unsaturated polyester
The montmorillonite of 14g is added in the unsaturated polyester (UP) of 136g, is uniformly mixed, mixing temperature is 20 DEG C~30
DEG C, mixing time is 10min~20min, obtains solution B；
It is 7: 2 by montmorillonite and zinc borate mass ratio, the zinc borate of 4g is added in above-mentioned solution B, is stirred
Even, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution C；
It is 1: 5 by zinc borate and methyl acid phosphate diformazan rouge mass ratio, two formicester of methyl acid phosphate of 20g is added to above-mentioned molten
It in liquid B, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution D；
It is 11: 10 by ammonium polyphosphate modifying and methyl acid phosphate diformazan rouge mass ratio, the ammonium polyphosphate modifying of 22g is added to
It in above-mentioned solution D, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, is obtained molten
Liquid；The benzoyl peroxide initiator that 4g is added in solution again obtains solution E after mixing evenly.
It is put into drying box after solution E is infused film, for the first time with 80 DEG C of dry 1 hours；Second with 110 DEG C of solidifications 3
Hour, it demoulds and takes out after being cooled to room temperature, obtain modified unsaturated polyester.Solidify the typical performance of unsaturated polyester (UP) respectively referring to
Attached drawing 2.
Referring to attached drawing 2, it is composite flame-proof modified unsaturated polyester provided by the invention and the pure insatiable hunger that comparative example 1 provides
With the oxygen index (OI) test result figure of polyester.The oxygen index (OI) of example 7 is 28.17.
Embodiment 8
1, the preparation of composite flame-retardant agent modified unsaturated polyester
The montmorillonite of 18g is added in the unsaturated polyester (UP) of 136g, is uniformly mixed, mixing temperature is 20 DEG C~30
DEG C, mixing time is 10min~20min, obtains solution B；
It is 9: 2 by montmorillonite and zinc borate mass ratio, the zinc borate of 4g is added in above-mentioned solution B, is stirred
Even, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution C；
It is 1: 5 by zinc borate and methyl acid phosphate diformazan rouge mass ratio, two formicester of methyl acid phosphate of 20g is added to above-mentioned molten
It in liquid C, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, obtains solution D；
It is 9: 10 by ammonium polyphosphate modifying and methyl acid phosphate diformazan rouge mass ratio, the ammonium polyphosphate modifying of 18g is added to
It in above-mentioned solution D, is uniformly mixed, mixing temperature is 20 DEG C~30 DEG C, and mixing time is 10min~20min, is obtained molten
Liquid；The benzoyl peroxide initiator that 4g is added in solution again obtains solution E after mixing evenly.
It is put into drying box after solution E is infused film, for the first time with 80 DEG C of dry 1 hours；Second with 110 DEG C of solidifications 3
Hour, it demoulds and takes out after being cooled to room temperature, obtain modified unsaturated polyester.Solidify the typical performance of unsaturated polyester (UP) respectively referring to
Attached drawing 2.
Referring to attached drawing 2, it is composite flame-proof modified unsaturated polyester provided by the invention and the pure insatiable hunger that comparative example 1 provides
With the oxygen index (OI) test result figure of polyester.The oxygen index (OI) 28.17 of example 8.In example 7 compared with example 8, they have identical oxygen
Index, it can be seen that the obvious synergistic effect between ammonium polyphosphate modifying and montmorillonite.From example 5 to example 8, with modified poly-
The reduction of ammonium phosphate amount and the increase of montmorillonite amount, oxygen index value reduce, and reflect the high-efficient of ammonium polyphosphate modifying fire retardant
In montmorillonite.With the increase of montmorillonite, oxygen index (OI) is gradually reduced.The dispersion of montmorillonite and aggregation difference will be such that composite material reaches
To layered structure.It is flammable therefore improve that as was expected when adding excessive montmorillonite.
Claims (4)
1. a kind of method of composite flame-retardant agent modified unsaturated polyester, specifically includes the following steps:
(1) ammonium polyphosphate is uniformly mixed under agitation with unsaturated polyester (UP) in mass ratio 1: 1；
(2) initiator is added into step (1) resulting solution under agitation, obtains solution A；
(3) it is put into drying box after solution A being infused film, pulverizes and sieves after solidification, obtains ammonium polyphosphate modifying；
(4) montmorillonite is mixed under agitation with unsaturated polyester (UP), both control mass ratio is (1~9): 68, temperature is
20 DEG C~30 DEG C, mixing time is 10min~20min, obtains solution B after mixing；
(5) zinc borate is mixed under agitation with step (4) resulting solution B, in control zinc borate dosage and step (4)
The mass ratio of montmorillonite is 2: (1~9), temperature are 20 DEG C~30 DEG C, and mixing time is 10min~20min, after mixing
To solution C；
(6) two formicester of methyl acid phosphate is added in solution C under agitation, in control two formicester of methyl acid phosphate and step (5)
Zinc borate mass ratio be 5: 1, temperature be 20 DEG C~30 DEG C, mixing time be 10min~20min, obtain after mixing
Solution D；
(7) step (3) resulting ammonium polyphosphate modifying is added in solution D under agitation, control ammonium polyphosphate modifying with
The mass ratio of two formicester of methyl acid phosphate is (9~17) in step (6): 10, temperature is 20 DEG C~30 DEG C, mixing time 10min
~20min, obtains solution after mixing；
(8) initiator will be added in step (7) resulting solution, obtains solution E, be put into drying box after infusing film, respectively at 80 DEG C,
Dry 1h and 3h at 110 DEG C, cooling and demolding is to get arriving a kind of modified unsaturated polyester.
2. the method according to claim 1, wherein the initiator is benzoyl peroxide.
3. the method according to claim 1, wherein the granularity of the ammonium polyphosphate modifying is 300~400
Mesh.
4. the method according to claim 1, wherein the mass ratio of the unsaturated polyester (UP) and composite flame-retardant agent is
(70~100): 30.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379078A (en) * | 2002-04-18 | 2002-11-13 | 巴陵石化岳阳石油化工总厂 | Process for preparing micro-encapsulated expansion-type N-P flame-retarding agent |
| WO2014209583A1 (en) * | 2013-06-28 | 2014-12-31 | Sabic Innovative Plastics Ip B.V. | Intumescent coating composition comprising particulate poly(phenylene ether) |
| CN106147104A (en) * | 2015-03-10 | 2016-11-23 | 天津工业大学 | A kind of flame-retarded unsaturated polyester resin and enhancing method of modifying thereof |
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2017
- 2017-11-08 CN CN201711118764.0A patent/CN109749383A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379078A (en) * | 2002-04-18 | 2002-11-13 | 巴陵石化岳阳石油化工总厂 | Process for preparing micro-encapsulated expansion-type N-P flame-retarding agent |
| WO2014209583A1 (en) * | 2013-06-28 | 2014-12-31 | Sabic Innovative Plastics Ip B.V. | Intumescent coating composition comprising particulate poly(phenylene ether) |
| CN106147104A (en) * | 2015-03-10 | 2016-11-23 | 天津工业大学 | A kind of flame-retarded unsaturated polyester resin and enhancing method of modifying thereof |
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Application publication date: 20190514 |