CN109485918A - A kind of Halogen phosphorus series composite flame retardant and flame-retardant high-molecular composite material - Google Patents
A kind of Halogen phosphorus series composite flame retardant and flame-retardant high-molecular composite material Download PDFInfo
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- CN109485918A CN109485918A CN201811444282.9A CN201811444282A CN109485918A CN 109485918 A CN109485918 A CN 109485918A CN 201811444282 A CN201811444282 A CN 201811444282A CN 109485918 A CN109485918 A CN 109485918A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 60
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- -1 Halogen phosphorus series Chemical class 0.000 title claims abstract description 25
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 16
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 16
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 16
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 8
- 239000004615 ingredient Substances 0.000 claims abstract description 8
- 239000002808 molecular sieve Substances 0.000 claims abstract description 8
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 4
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 239000000779 smoke Substances 0.000 abstract description 8
- 229920002521 macromolecule Polymers 0.000 abstract description 5
- HBADPDCSYBNJLK-UHFFFAOYSA-N P(=O)(O)(O)OCC(CO)(CO)CO.C(C=C)(=O)O Chemical compound P(=O)(O)(O)OCC(CO)(CO)CO.C(C=C)(=O)O HBADPDCSYBNJLK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 239000012757 flame retardant agent Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920006778 PC/PBT Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 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 description 2
- 238000007707 calorimetry Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 206010003497 Asphyxia Diseases 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 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
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000000003 thermogravimetry coupled to Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
A kind of Halogen phosphorus series composite flame retardant and flame-retardant high-molecular composite material.The ingredient of Halogen phosphorus series composite flame retardant by mass percentage, acrylic acid pentaerythritol phosphate: 1~30%, ammonium polyphosphate: 0~60%, polyphosphoric acid melamine: 0~50%, molecular sieve: 0~25%.The ingredient of flame-retardant high-molecular composite material by mass percentage, Halogen phosphorus series composite flame retardant: 20~50%, high molecular material: 49.9~79.7%, antioxidant: 0.1~0.3%.The limit oxygen index of the flame-retardant high-molecular composite material reaches as high as 46.7%, UL-94 vertical burn test reaches V-0 grade, and heat release rate (HRR) and always raw smoke (TSR) can reduce by 84.0% and 43.02% compared with substrate macromolecule material respectively.
Description
Technical field
The invention belongs to technical field of flame retardant, and in particular to a kind of Halogen phosphorus series composite flame retardant and flame-retardant high-molecular are multiple
Condensation material.
Background technique
With the development of economy, more and more high molecular materials enter among the production and living of people, clothing ,food and housing
Row is used, its figure is seen everywhere.However most high molecular material limit oxygen index are below 21%, belong to combustible material.
2015, national public security fire-fighting department was informed of a case fire 34.7 ten thousand altogether, dead 1899 people, injured 1213 people, direct property loss
43.6 hundred million yuan (Kunming Fire Department of Ministry of Public Security China fire yearbook .2016 [M]: Yunnan Publishing Group, 2016,03-04.),
In be much related to high molecular material.High molecular material is not easy to extinguish once burning, and largely smolders, and high temperature dropping easily ignites
Other materials.Carrying out flame retardant treatment to high molecular material is to reduce fire hazard, extends personnel's escape time, reduces fire hazard
Effective means.
Halogen flame is a kind of traditional fire retardant, is continuously generated hydrogen halide in a fire, is also diluted flammable
Property gas, due to gas have biggish density, be covered on combustible surface, also obstructed the contact with oxygen, destroy combustion
Burn needed for element, be unable to reach burning condition, thus reach fire-retardant purpose (Environment international,
2003,29(6):683-689.).But halogen flame combustion process releases a large amount of black smokes and poisonous gas hydrogen halides, and its
It is easily generated in air that there is corrosive strong acid halogen acids, seriously endanger human health and environment.According to fire incident
Casualties statistics, 70~80% people is because sucking smog and toxic gas lead to death by suffocation.
Metal hydroxides based flame retardant is mainly magnesium hydroxide (MH) and aluminium hydroxide (ATH) fire retardant.Their resources
It is rich and easy to get, cheap, stability is good, nontoxic, corrosion-free.It is filled into matrix, not only there is fire-retardant effect, and
And there are also suppression cigarette effect, safety and environmental protections (Polymer international, 2010,59 (4): 539-542.).If but wanting
Achieved the effect that with metal hydroxides flame-retardant polymer relatively good, their additive amount has generally all reached 50~60%, this
The processing performance and mechanical property of material are had lost to a certain extent.
Phosphorus is a kind of for fire-retardant general effective element, it is possible to replace still widely used halogen flame at present.
Wu et al. is prepared for the ammonium polyphosphate with the microencapsulation of melamino-formaldehyde (MF) resin by in-situ polymerization
Salt (MCAPP), the results showed that, less granular size and water absorption rate can be subtracted with MF resin microcapsuleization.In identical additive amount
Under the conditions of compared with PP/APP composite material, the LOI value of PP/MCAPP composite material increases to 30.5% (Polymer from 20%
Composites,2008,29(8):854-860.)。
Wang et al. has studied double-shell microcapsule polyphosphoric acid ammonium salt (APP).By situ aggregation method use by urea-formaldehyde
With the duplex shell structure microencapsulation APP (MUFAPP) of melamine formaldehyde resin composition.It has been investigated that adding 30% in PP
APP, UL-94 test cannot reach any grade, and in PP be added 30% MUFAPP UL-94 test in can achieve
V-1 grades.When MUFAPP additive amount increases to 40%, the UL-94 result of PP/MUFAPP is increased to V-0 grades of (Journal of
Thermal Analysis and Calorimetry,2014,115(2):1173-1181.)。
Liu et al. improves bisphenol-A by addition resorcinol bis- (diphenyl phosphoesters) (RDP) and poly- (phenylate) (PPO)
Polycarbonate (PC)/poly- (mutual-phenenyl two acid bromide two alcohol ester) (PBT) blend flame retardant property.Pass through TGA, FTIR, TGA-
Analysis is studied in detail to the fire-retardant of PC/PBT/RDP and PC/PBT/RDP/PPO blend in FTIR and SEM etc., as a result
Show that RDP can be induced at 450 DEG C and generate higher coke yield, improves the thermal stability with PPO mixture.In addition, RDP
So that the anti-flammability of PC/PBT blend is obtained more significant raising with being applied in combination for PPO, and reaches the sample of 1.6mm thickness
V-0 grade (Polymers for Advanced Technologies, 2011,22 (12): 2392-2402.).
Luo etc. synthesizes a kind of phosphorous and nitro fire retardant --- three (3- nitrobenzophenone) phosphine (NPPh3), and by itself and phosphorus
Triphenyl phosphate ester (TPP) mixing, is used for Flame-retardant acrylonitrile-butadiplasticrene (ABS).Show ABS/ by LOI and UL-9 test
NPPh3/ TPP composite material be used only ABS/NPPh3It is compared with the system of ABS/TPP, ABS/NPPh3The LOI of/PP is higher.This
Outside, its gas generated in thermal degradation process is had studied by TG-FTIR, the results showed that ABS/NPPh3/ TPP has cohesion
Phase and gas phase cooperative flame retardant effect, and NPPh3/ TPP improves thermal stability (the Journal of Thermal of ABS
Analysis and Calorimetry,2018,132(1):263-273.)。
The above phosphorus flame retardant achieves good flame retardant effect, however is limited in that its core flame-retardant compound closes
It is typically more complicated at process, it is unfavorable for industrialized production, final products cost greatly improved, limit these fire retardants
Using.
Summary of the invention
The purpose of the present invention is to overcome above-mentioned the shortcomings of the prior art, provides a kind of Halogen phosphorus series composite flame retardant,
Ingredient includes acrylic acid pentaerythritol phosphate (PEPAA), ammonium polyphosphate (APP), polyphosphoric acid melamine (MPP) and molecule
Sieve, the good flame retardation effect of the Halogen phosphorus series composite flame retardant are at low cost.
Another object of the present invention provides a kind of flame-retardant high-molecular composite material.
Above-mentioned purpose of the invention, is achieved by following technical solution:
A kind of Halogen phosphorus series composite flame retardant, ingredient by mass percentage, acrylic acid pentaerythritol phosphate: 1~
30%, ammonium polyphosphate: 0~60%, polyphosphoric acid melamine: 0~50% and molecular sieve: 0~25%.
The preparation method of the Halogen phosphorus series composite flame retardant includes the following steps: to incite somebody to action according to ingredient percent
Acrylic acid pentaerythritol phosphate, ammonium polyphosphate, polyphosphoric acid melamine and molecular sieve are blended, and it is compound to obtain Halogen phosphorus system
Fire retardant.
A kind of flame-retardant high-molecular composite material, ingredient by mass percentage, Halogen phosphorus series composite flame retardant: 20~
50%, high molecular material: 49.9~79.7%, antioxidant: 0.1~0.3%.
The high molecular material is one of plastics or rubber or a variety of.
The limit oxygen index of the flame-retardant high-molecular composite material is that 29~46.7%, UL-94 vertical burn test is
V-1 ratings above, heat release rate (HRR) and total life smoke (TSR) reduce by 22~84.0% compared with substrate macromolecule material respectively
With 12.1~43.02%.
The preparation method of the flame-retardant high-molecular composite material, include the following steps: Halogen phosphorus series composite flame retardant and
Macromolecule material particle is blended, and obtains that sample is blended, and sample will be blended and carry out 10~20min of melt blending, melt blending
Sample afterwards, it is tabletted, obtain flame-retardant high-molecular composite material.
The equipment of the melt blending operation is mixer, revolving speed 50r/min.
The equipment of the tabletted operation is vulcanizing press.
Beneficial effects of the present invention:
1, on the one hand is Halogen phosphorus series composite flame retardant of the invention, which passes through, added PEPAA, with ammonium polyphosphate, polyphosphoric acid trimerization
Cyanamide, molecular sieve generate synergistic fire retardation, greatly improve flame retarding efficiency, reduce combustion product gases production quantity；On the other hand poly- phosphorus
The use of sour ammonium, polyphosphoric acid melamine and molecular sieve also reduces the dosage of synthesis fire retardant PEPAA, to significantly reduce
Production cost, convenient for the popularization and use of the fire retardant；
2, Halogen phosphorus series composite flame retardant of the invention and high molecular material are compound, obtain flame-retardant high-molecular composite material,
The flame-retardant high-molecular composite material is fire retardant, and self-extinguishing without fire is without dripping off, halogen-free, and oxygen toxicity is big compared with halogen fire proofing
Width reduces, and the limit oxygen index of the flame-retardant high-molecular composite material reaches V- up to 27~46.7%, UL-94 vertical burn test
1 ratings above, heat release rate (HRR) and total life smoke (TSR) reduce 22~84.0% compared with substrate macromolecule material respectively
With 12.1~43.02%.
Detailed description of the invention
Fig. 1 is the high molecular material and the polyacrylic heat of Comparison study example 4 of 1~3 composite flame-retardant agent of Application Example preparation
Rate of release comparison diagram；
Fig. 2 is that high molecular material prepared by 1~3 composite flame-retardant agent of Application Example and Comparison study example 4 are polyacrylic total
Raw smoke comparison diagram.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and specific embodiment is that this is further described
Invention, non-limiting protection scope of the present invention.
It is illustrated in a manner of specific embodiment below, the raw material is mass percent.
Prepare embodiment
In the ratio that table 1 is recorded, the composite flame-retardant agent of Examples 1 to 6 is prepared.
Table 1
In the ratio that table 2 is recorded, comparative example 1~4 is prepared.
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| PEPAA | - | - | - | - |
| APP | 100% | - | 50% | - |
| MPP | - | 100% | 50% | - |
| Molecular sieve | - | - | - | - |
| Polypropylene | - | - | - | 100% |
Application Example
In the ratio that table 3 is recorded, the flame-retardant high-molecular composite wood of application and preparation Examples 1 to 6 and Comparison study example 1~4
Expect, the composite flame-retardant agent in table 3 corresponds to the composite flame-retardant agent prepared in table 1 and table 2.
Table 3
| Composite flame-retardant agent | Antioxidant | Polypropylene | Nylon 11 | Butadiene-styrene rubber | Polystyrene | |
| Application Example 1 | 30% | 0.3% | 69.7% | - | - | - |
| Application Example 2 | 28% | 0.3% | 71.7% | - | - | - |
| Application Example 3 | 25% | 0.3% | 74.7% | - | - | - |
| Application Example 4 | 20% | 0.3% | - | 79.7% | - | - |
| Application Example 5 | 29.7% | 0.3% | - | - | 70% | - |
| Application Example 6 | 49.7% | 0.3% | - | - | - | 50% |
| Comparison study example 1 | 50% | 0.3% | 49.7% | - | - | - |
| Comparison study example 2 | 50% | 0.3% | 49.7% | - | - | - |
| Comparison study example 3 | 50% | 0.3% | 49.7% | - | - | - |
| Comparison study example 4 | - | - | 100% | - | - | - |
The flame retardant property such as table 4 of Application Example and Comparison study example.
Table 4
The high molecular material and the polyacrylic heat release speed of Comparison study example 4 of 1~3 composite flame-retardant agent of Application Example preparation
Rate comparison diagram, as shown in Figure 1, effectively reducing heat release rate；The macromolecule of 1~3 composite flame-retardant agent of Application Example preparation
Material and the polyacrylic total raw smoke comparison diagram of Comparison study example 4, as shown in Fig. 2, effectively reducing total raw smoke.
By Comparison study example it is found that when high molecular material is without flame retardant treatment compared with Application Example test data
When, it easily burns and largely discharges poisonous and harmful flue gas.And APP, MPP or APP/MPP mixture is used alone as fire retardant
When, flame retardant effect is poor, and limit oxygen index is less than 26%, and UL-94 is without classification, though heat release rate and total raw smoke
Purer high molecular material makes moderate progress, but effect is limited.PEPAA is only added, collectively forms and cooperates with APP, MPP, molecular sieve
When fire retardant, flame retardant effect is good, and it is (most of for V-0 that limit oxygen index reaches V-1 grades or more rank more than 29%, UL-94
Grade), without dripping off, heat release rate and total raw purer high molecular material of smoke decline to a great extent.
Claims (3)
1. a kind of Halogen phosphorus series composite flame retardant, which is characterized in that its ingredient by mass percentage, acrylic acid pentaerythrite phosphoric acid
Ester: 1~30%, ammonium polyphosphate: 0~60%, polyphosphoric acid melamine: 0~50%, molecular sieve: 0~25%.
2. a kind of flame-retardant high-molecular composite material, which is characterized in that its ingredient by mass percentage, Halogen phosphorus system composite flame-proof
Agent: 20~50%, high molecular material: 49.9~79.7%, antioxidant: 0.1~0.3%.
3. flame-retardant high-molecular composite material according to claim 2, which is characterized in that the high molecular material is plastics
Or one of rubber or a variety of.
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