CN104861206A - Coated flame retardant, preparation method and application thereof, as well as high polymer composition comprising coated flame retardant - Google Patents
Coated flame retardant, preparation method and application thereof, as well as high polymer composition comprising coated flame retardant Download PDFInfo
- Publication number
- CN104861206A CN104861206A CN201510340262.7A CN201510340262A CN104861206A CN 104861206 A CN104861206 A CN 104861206A CN 201510340262 A CN201510340262 A CN 201510340262A CN 104861206 A CN104861206 A CN 104861206A
- Authority
- CN
- China
- Prior art keywords
- fire retardant
- type fire
- cladded type
- carbonate
- flame retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a coated flame retardant. The coated flame retardant comprises a carbonate core material of which the particle diameter is 1-90 micrometers; the outer surface of the core material is coated with a coating layer of a dialkyl phosphinate flame retardant; the preferential particle diameter of the carbonate core material is 15-50 micrometers. Carbonate in the coated flame retardant serves as a synergistic agent for dialkyl phosphinate; a high polymer composition added with the coated flame retardant is low in heat release and smoke level in a combustion process, and the corrosion of the high polymer composition added with the coated flame retardant to a threaded rod of processing equipment is reduced; moreover, through the adoption of the coated flame retardant, the dialkyl phosphinate flame retardant and carbonate can be efficiently compounded, so that the problem that a compound flame retardant mixture cannot uniformly disperse in resin is solved, and the synergistic effect of the dialkyl phosphinate flame retardant and carbonate can be exerted to the greatest extent and better than that of the compound flame retardant mixture.
Description
Technical field
The invention belongs to pluronic polymer field, relate to a kind of cladded type fire retardant, be specifically related to the cladded type fire retardant that surface that dialkylphosphinic salts fire retardant is coated on carbonate is formed, and the preparation method of this cladded type fire retardant and application and consisting of polymeric compositions.
Background technology
After organic synthesis macromolecular material widely uses, namely the mankind start to face new fire threat, and reason is this kind of material overwhelming majority is inflammable or flammable.So add fire retardant in the material to become fire preventing generation, reduce one of feasibility and necessity measure of fire hazard.But according to data statistics, in fire, fatalities major part is because toxic and harmful and suffocating of cigarette are caused, so but cigarette, attenuation are mentioned in the same breath with fire-retardant.Halogen-free flame retardants replaces gradually halogen fire retardant, is widely used in macromolecular material, just in order to ensure, under fire-retardant prerequisite, to reach the effect pressing down cigarette, attenuation.
Dialkylphosphinic salts is as the efficient phosphorus series non-halogen fire retardant of one, and have amount of flame-retardant agent little, moulding compound good mechanical property, color and luster is good, and smoke density is low, the feature that CTI value is high.Be added with in the polymeric compositions combustion processes of dialkylphosphinic salts; dialkylphosphinic salts can reduce the decomposition temperature of polymeric compositions greatly; polymeric compositions is impelled to decompose in advance; layer of charcoal can be formed at a lower temperature; polymeric compositions under protection layer of charcoal can not be ignited at a higher temperature, thus plays good flame retardant effect.Successively have studied alkyl phosphinic acid zinc/aluminium/calcium does the performance of fire retardant in PA and PBT to Ticona company of the U.S., show that the addition of methylethyl phospho acid aluminium/calcium in PBT is 15% and addition in PA when being 20%, the fire-retardant rank of UL94 V-0 can be reached.Regrettably, because dialkylphosphinic salts reaches fire-retardant object by impelling polymeric compositions to resolve into charcoal in advance, this is in incomplete combustion state when just causing fire-retardant polymeric compositions to burn, and produce a large amount of cigarettes, and release a large amount of heat in the starting stage of burning, add the fatalities in fire to a certain extent.
In order to solve the raw cigarette problem that fire-retardant polymeric compositions incomplete combustion brings, give multiple solution in first technology.CN103724967A adds Compositional type auxiliary agent and solves the large problem of raw smoke which in flame-retarded resin, this Compositional type auxiliary agent is made up of the following component by intermingling material weight percent: magnesium hydroxide 0.5wt%-4wt%, zinc borate 1wt%-6wt%, molecular sieve activation powder 1wt%-5wt%, by magnesium hydroxide, zinc borate, the mixing of molecular sieve activation powder, stir, i.e. this Compositional type auxiliary agent obtained.CN101591468A adds in resin system: the low promotor of being fuming of fumicants and 1wt%-6wt% falls in the compound of 0.2wt%-2wt%.
Meanwhile, when dialkylphosphinic salts is applied to high-temperature nylon or polyester, the moulding compound being added with dialkylphosphinic salts can produce heavy corrosion to the metal parts of processing unit (plant) in the course of processing.（US 20110021676A1）。
In order to solve the problem that moulding compound corrodes processing unit (plant) metal parts, patent US 20110021676A1 is by together with composite for the metal-salt of dialkylphosphinic salts and organic acid or mineral acid, be applied in nylon or polyester, relative to the nylon or the polyester that are used alone dialkylphosphinic salts, substantially increase its mobility, and alleviate the corrosion of moulding compound to processing unit (plant) metal parts to a certain extent.But various fire retardant is just carried out mechanical-physical mixing by compound flame redundant in above-mentioned patent (US 20110021676A1) in use or prior to use, there is the problem that dispersion is uneven, and due to the metal-salt addition of organic acid or mineral acid large, poor with material compatibility, can grievous injury moulding compound mechanical property.
Above prior art is all in use or prior to use fire retardant and auxiliary agent are carried out mechanical-physical mixing, general all exist the uneven problem of dispersion, the synergistic effect between each component can not be played completely, may impact the performance of polymkeric substance other side.
Summary of the invention
Primary and foremost purpose of the present invention is the cladded type fire retardant providing a kind of dialkylphosphinic salts fire retardant carbon coated hydrochlorate, when this cladded type fire retardant is applied to high polymers composition, the raw smoke which in fire-retardant polymeric compositions combustion processes and heat release amount can be reduced to a great extent.Meanwhile, this cladded type fire retardant achieves the high efficiency composition of dialkylphosphinic salts fire retardant and carbonate, effectively can solve the problem that compound flame redundant dispersion is uneven, improve the homogeneity of fire-retardant polymeric compositions performance.And when this cladded type fire retardant is applied to high polymers composition, the corrosion to processing unit (plant) screw rod in the high polymers composition course of processing can be alleviated to a great extent.
Another object of the present invention is to provide the preparation method of above-mentioned cladded type fire retardant.
Another object of the present invention is to provide the purposes of above-mentioned cladded type fire retardant.
Another object of the present invention is to provide the polymeric compositions comprising above-mentioned cladded type fire retardant.
The present invention is achieved by the following technical solutions:
A kind of cladded type fire retardant, is the core of the carbonate of 1 μm ~ 90 μm containing particle diameter, is coated with the coating layer of dialkylphosphinic salts fire retardant at the outside surface of core; The core particle diameter of described carbonate is preferably 15 μm ~ 50 μm.
Described core and coating layer mass ratio are 1:100 ~ 60:100.Preferably, described core and coating layer mass ratio are 10:100 ~ 45:100.The cladded type fire retardant of the core described in non-invention and coating layer mass ratio, when being applied to polymeric compositions, in combustion processes, heat release amount is large, and raw smoke which is many, large to the extent of corrosion of processing unit (plant) screw rod.
Wherein, the particle diameter of described cladded type fire retardant is 5 μm ~ 150 μm; Be preferably 15 μm ~ 90 μm; Be more preferably 25 μm ~ 70 μm.
Wherein, the water ratio of described cladded type fire retardant is 0.01 wt% ~ 10wt%, is preferably 0.1 wt% ~ 1wt%.
Wherein, the tap density of described cladded type fire retardant is 50 g/L ~ 850g/L, is preferably 200 g/L ~ 650g/L.
Wherein, the solubleness of described cladded type fire retardant in water, organic solvent or water and ORGANIC SOLVENT MIXTURES is 0.005wt% ~ 9.99wt%.
Wherein, described organic solvent is one or more the mixture in alcohol, ether, ketone, carboxylic acid, ester, aliphatic hydrocarbon, alicyclic hydrocarbon polymer, aromatic hydrocarbons, halohydrocarbon.Be preferably one or more mixtures in methyl alcohol, ethanol, ethylene glycol, ether, glycol ether, acetone, acetic acid, ethyl acetate, normal hexane, benzene, toluene, hexanaphthene, chloroform, tetracol phenixin.
Wherein, described carbonate is selected from one or more mixtures in carbonic acid normal salt, acid carbonate, subcarbonate; Described carbonic acid normal salt is selected from one or more mixtures in magnesiumcarbonate, zinc carbonate, water-ground limestone, light calcium carbonate, is preferably magnesiumcarbonate, light calcium carbonate; Described acid carbonate is selected from one or more mixtures in Magnesium hydrogen carbonate, Calcium hydrogen carbonate, sodium bicarbonate, is preferably Calcium hydrogen carbonate; Described subcarbonate is selected from one or more mixtures in ventilation breather, zinc subcarbonate, magnesium basic carbonate, is preferably zinc subcarbonate.
Wherein, described dialkylphosphinic salts fire retardant has such as formula the molecular structure shown in I:
Wherein, R
1, R
2identical or different, be expressed as straight or branched C1-C6 alkyl;
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr or Mn;
M is 2-4.
Preferably, described R
1, R
2identical or different, be methyl, ethyl, propyl group, butyl, hexyl.
Preferably, described M is Mg, Ca, Al, Zn.
More preferably, described dialkylphosphinic salts is selected from one or more mixtures in aluminum diethylphosphinate, dipropyl phospho acid aluminium, dibutyl phospho acid zinc, dihexyl phospho acid magnesium, ethyl-butyl phospho acid calcium; Be preferably aluminum diethylphosphinate.
A preparation method for above-mentioned cladded type fire retardant, comprises the steps:
A) carbonate is dispersed in water, makes suspension;
B) the dialkylphosphinic salts aqueous solution, the metallic compound aqueous solution are added in suspension carry out coating reaction;
C) by the filtration of coating reaction product, washing, drying, cladded type fire retardant is obtained.
Wherein, described coating reaction refers to that dialkylphosphinic salts aqueous solution metallizing thing reactant aqueous solution generates precipitation, and the precipitation generated is attached to the surface of carbonate core, forms coating reaction product.
Wherein, described dialkyl phosphinic acid/salt is one or more mixtures in diethyl phospho acid sodium/potassium, dipropyl phospho acid sodium/potassium, dibutyl phospho acid sodium/potassium, ethyl-butyl phospho acid sodium/potassium, dihexyl phospho acid sodium/potassium; Be preferably diethyl phospho acid sodium.
Wherein, described metallic compound is selected from one or more in the compound of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr or Mn; Be preferably one or more in the compound of Mg, Ca, Al or Zn; Be more preferably the compound of Al.
Wherein, described step a), b), c) in, the temperature of disperse, add, react, filter, washing is 0-100 DEG C, dry temperature is 80 DEG C-230 DEG C.
The invention also discloses the purposes of above-mentioned cladded type fire retardant as fire retardant.
The invention also discloses the polymeric compositions comprising above-mentioned cladded type fire retardant.Wherein, described polymeric compositions comprises 5 wt% ~ 25 wt% cladded type fire retardants, 45 wt% ~ 80 wt% superpolymer or its mixtures.
Wherein, described superpolymer is one or more the mixture in PA, PBT, PET, PPE, TPEE, HTPA; Be preferably one or more mixtures in PA, PBT, PPE, HTPA.
Wherein, described polymeric compositions, according to the demand of material different performance, can add the glass fibre of 0 ~ 30 wt% or the auxiliary agent of filler and 0 ~ 5wt%.
Filler of the present invention is the material being commonly used to strengthening or filled polymer, also can use the mixture of two or more mineral filler and/or toughener.Filler can comprise following one or more: glass fibre, glass flake, kaolin, clay, talcum powder, wollastonite, calcium carbonate, silicon-dioxide, carbon fiber, potassium titanate etc.
Described processing aid can be do not disturb the aforementioned additional component that character still improves other beneficial property of wishing, as antioxidant, lubricant, releasing agent, nucleator, toner, photostabilizer.
The present invention compared with prior art, has following beneficial effect:
1) cladded type fire retardant of the present invention, is coated on carbonate core surfaces using dialkylphosphinic salts as shell, when being applied to high polymers composition, can reduce the raw smoke which in fire-retardant high polymers composition burn process and heat release amount to a great extent.
2), when cladded type fire retardant of the present invention is applied to high polymers composition, the corrosion to processing unit (plant) screw rod in the high polymers composition course of processing can be alleviated to a great extent.
3) cladded type fire retardant of the present invention, dialkylphosphinic salts is coated on carbonate builders surface, achieve the high efficiency composition of dialkylphosphinic salts and carbonate, effectively can solve the problem that compound flame redundant dispersion is uneven, improve the homogeneity of fire-retardant polymeric compositions performance, reduce the impact on other performance of polymer composition.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of light calcium carbonate.
Fig. 2 is the energy spectrogram of light calcium carbonate.
Fig. 3 is the constituent content table in light calcium carbonate energy spectrogram.
Fig. 4 is the electron scanning micrograph of aluminum diethylphosphinate.
Fig. 5 is the energy spectrogram of aluminum diethylphosphinate.
Fig. 6 is the constituent content table in aluminum diethylphosphinate energy spectrogram.
The electron scanning micrograph of the cladded type fire retardant of Fig. 7 prepared by the embodiment of the present invention 2.
The energy spectrogram of the cladded type fire retardant of Fig. 8 prepared by the embodiment of the present invention 2.
Constituent content table in the cladded type fire retardant energy spectrogram of Fig. 9 prepared by the embodiment of the present invention 2.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.The person skilled in the art in this field is according to the content of the invention described above, and improvement and the adjustment of non-intrinsically safes more made for the present invention still belong to protection scope of the present invention.
Now following explanation is done to starting material selected in embodiment and comparative example, but is not limited to these materials:
PBT:PBT 1100-211M(Taiwan Changchun group)
PA66:PA66 EP-158(Hua Feng group)
PA6:PA6 M2000(Meida Nylon Co., Ltd., Xinhui, Guangdong)
Asahi Chemical Industry of PPE:PPE 100Z(Japan)
HTPA：Amodel? A-6000（Solvay）
Glass fibre 1:ECS13-4.5-534(megalith group)
Glass fibre 2:ECS301-HP(Chongqing Polycomp International Co., Ltd);
Oxidation inhibitor: 1010, (Jin Haiyabao) oxidation inhibitor: 168(Jin Haiyabao)
Lubricant: the friendly auxiliary agent Chemical Co., Ltd. in GLYCOLUBE-P(Nanjing)
Releasing agent: silicone master batch (Dow Corning)
Nucleator: sarin (DUPONT)
Photostabilizer: 770(Ciba Specialty Chemicals)
The method that the present invention characterizes cladded type fire retardant pattern is scanning electron microscope (SEM).
The method that the present invention analyzes cladded type fire retardant surface composition is power spectrum (EDS).
The present invention's power spectrum (EDS) analyzes cladded type fire retardant surface composition, concrete operations: the SEM scanning area of sample is extended to 5000 times, utilizes EDS to scan area S=100 μm in SEM figure
2sample in region, obtains the energy spectrogram of this surface area sample surfaces composition.The element that peak represents existence can be composed, the concentration of each element of the atomic mass per-cent representative composition specimen material of element in spectrogram.
The testing method of cladded type fire retardant of the present invention and core particle diameter is as follows:
Laser particle analyzer is utilized to test dispersion cladded type fire retardant in the liquid phase and the size distribution of core.Concrete operations are: according to the size of cladded type fire retardant and core, get 0.05g ~ 1.0g sample in beaker, add the mixing solutions dispersed with stirring of alcohol and water, pour in laser particle analyzer, after about 1min, the size distribution of cladded type fire retardant and core can be recorded.The D(50 that the size of cladded type fire retardant of the present invention and core records using laser particle analyzer) as Appreciation gist.
Cladded type fire retardant tap density testing method of the present invention measures with reference to GB20316.2-" mensuration of tap density ".
The testing method of cladded type fire retardant water ratio of the present invention measures with reference to GBT 6284-2006-" the universal method loss on drying of moisture determination in Chemicals ".
The testing method of cladded type fire retardant solubleness of the present invention is null readings.Concrete operations are: 25 DEG C, add in solution by cladded type fire retardant, and constant temperature stirs certain hour, leave standstill the composition of post analysis upper solution as the solubleness at this temperature.
Described solution refers in water, organic solvent or water and ORGANIC SOLVENT MIXTURES.
Raw smoke which (TSR) in the present invention in high polymers composition burn process and heat release amount (THR) are measured by cone calorimetry.Concrete testing standard and sample parameters as follows:
Testing standard: GB16172-2007-T.
Test parameter: sample size: 100mm x 100mm x 6mm; Radiation cone power 50kW/m
2.
TSR numerical value is larger, shows that in polymeric compositions combustion processes, raw smoke which is larger; THR numerical value is larger, shows that in polymeric compositions combustion processes, heat release amount is more.
In the present invention, non-glass fibre strengthens the TSR in PBT polymeric compositions combustion processes is 800 m
2/ m
2~ 1500m
2/ m
2; THR is 50 MJ/m
2~ 58MJ/m
2.
TSR in the present invention in 25% glass fiber reinforced PA66 polymeric compositions combustion processes is 1600 m
2/ m
2~ 2200m
2/ m
2; THR is 72 MJ/m
2~ 82MJ/m
2.
TSR in the present invention in 30% fiberglass reinforced PA 6/PPE alloy polymeric compositions combustion processes is 1100m
2/ m
2~ 1600m
2/ m
2; THR is 80 MJ/m
2~ 90MJ/m
2.
TSR in the present invention in 25% fiberglass reinforced PA 6 polymeric compositions thing combustion processes is 1400m
2/ m
2~ 2100m
2/ m
2; THR is 80 MJ/m
2~ 90MJ/m
2.
TSR in the present invention in 30% fiberglass reinforced HTPA polymeric compositions combustion processes is 1300m
2/ m
2~ 1800m
2/ m
2; THR is 89 MJ/m
2~ 97MJ/m
2.
The present invention evaluates the Corrosion Basis Screw Corrosion degree (Δ D) of polymeric compositions to processing unit (plant) screw rod and determines.The measuring method of Δ D is as follows:
When 100t fire-retardant polymeric compositions often processed by compounding combination unit, measure the diameter (D of same position screw rod before and after producing
beforeand D
after), calculate after producing the fire-retardant polymeric compositions of 100t, the difference DELTA D=D of screw diameter
before-D
after, Δ D value is larger, represents that Screw Corrosion is more serious.
In the present invention, non-glass fibre strengthens the Screw Corrosion degree Δ D of PBT polymeric compositions to compounding combination unit is 0.05 ~ 0.25mm.
In the present invention, the Screw Corrosion degree Δ D of 25% glass fiber reinforced PA66 polymeric compositions to compounding combination unit is 0.38mm ~ 0.70mm.
In the present invention, the Screw Corrosion degree Δ D of 30% fiberglass reinforced PA 6/PPE alloy polymeric compositions to compounding combination unit is 0.60 mm ~ 1.05mm.
In the present invention, the Screw Corrosion degree Δ D of 25% fiberglass reinforced PA 6 polymeric compositions to compounding combination unit is 0.40mm ~ 0.75mm.
In the present invention, the Screw Corrosion degree Δ D of 30% fiberglass reinforced HTPA polymeric compositions to compounding combination unit is 0.50mm ~ 0.80mm.
Notched Izod impact strength: GB 1843-2008.
Combustionproperty: UL94 Plastics Combustion performance test;
Use the test sample of thickness 1.5mm to measure UL 94 for the test sample from often kind of mixture to burn grade.Be below the burning grade that UL 94 specifies:
V-0: after batten leaves flame, the sustained combustion time, the sustained combustion temporal summation that 5 battens amount to when lighting for 10 times was no more than 50s, drips without molten drop no longer than 10s, flame is without spreading to fixture phenomenon, and the twilight sunset combustion time of sample after lighting end is no longer than 30s.
V-1: after batten leaves flame, the sustained combustion time, the sustained combustion temporal summation that 5 battens amount to when lighting for 10 times was no more than 250s no longer than 30s, and other standard is as V-0 no longer than 60s the twilight sunset combustion time after lighting end for sample.
, in sustained combustion process, there is molten drop in V-2: after batten leaves flame, the absorbent cotton indicator and molten drop can ignite, the same V-1 of other standard.
Unclassified (ncl): do not meet burning grade V-2.
comparative example 1-comparative example 5
Take aluminum diethylphosphinate, carbonate by the weight percent in table 1 in premixing machine, be uniformly mixed obtained compound flame redundant A1-A5.
Table 1 comparative example 1-5 (A1-A5) compound flame redundant composition constituent mass ratio
comparative example 6
A kind of cladded type fire retardant, containing particle diameter D(50) be the core of the magnesiumcarbonate of 15.37 μm, be coated with the coating layer of aluminum diethylphosphinate at the outside surface of core, wherein, the mass ratio of aluminum diethylphosphinate and magnesiumcarbonate is 100:0.5; The particle diameter D(50 of described cladded type fire retardant) be 29.87 μm; Water ratio is 0.14%; Tap density is 552g/L.
The preparation method of described cladded type fire retardant, comprises the steps:
A) get 5g magnesiumcarbonate to add in 995g water, be made into magnesiumcarbonate suspension;
B) be 0.5:100 by the mass ratio of magnesiumcarbonate core and aluminum diethylphosphinate coating layer, the diethyl phospho acid sodium water solution of 2769g 40% is added in magnesiumcarbonate suspension, in above-mentioned mixing solutions, add the aluminum sulfate aqueous solution of 1422g 60%, react and complete at 80 DEG C;
C) filtered by coating reaction product, wash, 80 DEG C of dryings, obtain cladded type fire retardant A6.
The EDAX results (characterizing with Conc) of A6 is as follows:
C：33.142 wt%；O：31.260 wt%； Al：8.860 wt%；P：26.579 wt%；Mg：0.159 wt%。
comparative example 7
A kind of cladded type fire retardant, containing particle diameter D(50) be the core of the light calcium carbonate of 21.43 μm, be coated with the coating layer of aluminum diethylphosphinate at the outside surface of core, wherein, the mass ratio of aluminum diethylphosphinate and light calcium carbonate is 100:65; The particle diameter D(50 of described cladded type fire retardant) be 33.56 μm; Water ratio is 0.21%; Tap density is 710g/L.
The preparation method of described cladded type fire retardant, comprises the steps:
A) get 125g light calcium carbonate to add in 125g water, be made into light calcium carbonate suspension;
B) be 65:100 by the mass ratio of light calcium carbonate core and aluminum diethylphosphinate coating layer, the diethyl phospho acid sodium water solution of 615g 30% is added in light calcium carbonate suspension, in above-mentioned mixing solutions, add the aluminum sulfate aqueous solution of 771g 20%, react and complete at 95 DEG C;
C) filtered by coating reaction product, wash, 230 DEG C of dryings, obtain cladded type fire retardant A7.
The EDAX results (characterizing with Conc) of A7 is as follows:
C：33.563 wt%；O：31.703 wt%； Al：7.624 wt%；P：25.917 wt%；Ca：1.193wt%。
embodiment 1
A kind of cladded type fire retardant, containing D(50) be the core of the magnesiumcarbonate of 15.37 μm, be coated with the coating layer of aluminum diethylphosphinate at the outside surface of core, wherein, the mass ratio of aluminum diethylphosphinate and magnesiumcarbonate is 100:1; The particle diameter D(50 of described cladded type fire retardant) be 30.88 μm; Water ratio is 0.11%; Tap density is 565g/L.
The preparation method of described cladded type fire retardant, comprises the steps:
A) get 10g magnesiumcarbonate to add in 990g water, be made into magnesiumcarbonate suspension;
B) be 1:100 by the mass ratio of magnesiumcarbonate core and aluminum diethylphosphinate coating layer, the diethyl phospho acid sodium water solution of 3692g 30% is added in magnesiumcarbonate suspension, in above-mentioned mixing solutions, add the aluminum sulfate aqueous solution of 1707g 50%, react and complete at 70 DEG C;
C) filtered by coating reaction product, wash, 150 DEG C of dryings, obtain cladded type fire retardant B1.
The EDAX results (characterizing with Conc) of B1 is as follows:
C：33.182 wt%；O：31.220 wt%； Al：8.858 wt%；P：26.481 wt%；Mg：0.259 wt%。
embodiment 2
A kind of cladded type fire retardant, containing particle diameter D(50) be the core of the light calcium carbonate of 21.43 μm, be coated with the coating layer of aluminum diethylphosphinate at the outside surface of core, wherein, the mass ratio of aluminum diethylphosphinate and light calcium carbonate is 100:60; The particle diameter D(50 of described cladded type fire retardant) be 30.12 μm; Water ratio is 0.15%; Tap density is 558g/L.
The preparation method of described cladded type fire retardant, comprises the steps:
A) get 100g light calcium carbonate to add in 100g water, be made into light calcium carbonate suspension;
B) be 60:100 by the mass ratio of light calcium carbonate core and aluminum diethylphosphinate coating layer, the diethyl phospho acid sodium water solution of 369g 50% is added in light calcium carbonate suspension, in above-mentioned mixing solutions, add the aluminum sulfate aqueous solution of 1542g 10%, react and complete at 60 DEG C;
C) coating reaction product filtered, wash, dry, obtain cladded type fire retardant B2.
The EDAX results (characterizing with Conc) of B2 is as follows:
C：33.538 wt%；O：31.025 wt%； Al：8.063 wt%；P：26.017 wt%；Ca：1.357 wt%。
embodiment 3
A kind of cladded type fire retardant, containing particle diameter D(50) be zinc subcarbonate, the D(50 of 18.43 μm) be the core of the magnesiumcarbonate mixture of 15.87 μm, the coating layer of aluminum diethylphosphinate is coated with at the outside surface of core, wherein, the mass ratio of zinc subcarbonate, magnesiumcarbonate mixture and aluminum diethylphosphinate coating layer is 5:40:100; The particle diameter D(50 of described cladded type fire retardant) be 40.66 μm; Water ratio is 0.35%; Tap density is 589g/L.
The preparation method of described cladded type fire retardant, comprises the steps:
A) get 11.1g zinc subcarbonate and 88.9g magnesiumcarbonate adds in 500g water, be made into zinc subcarbonate and magnesiumcarbonate suspension;
B) be 5:40:100 by the mass ratio of zinc subcarbonate, magnesiumcarbonate mixture core and aluminum diethylphosphinate coating layer, the diethyl phospho acid sodium water solution of 886g 50% is added in calcium carbonate and magnesiumcarbonate suspension, in above-mentioned mixing solutions, add the aluminum sulfate aqueous solution of 1138g 30%, react and complete at 100 DEG C;
C) filtered by coating reaction product, wash, 200 DEG C of dryings, obtain cladded type fire retardant B3.
The EDAX results (characterizing with Conc) of B3 is as follows:
C：33.354 wt%；O：31.514 wt%； Al：8.212 wt%；P：25.971 wt%；Zn：0.387 wt%；
Mg：0.562 wt%。
embodiment 4
A kind of cladded type fire retardant, containing D(50) be the core of the Calcium hydrogen carbonate of 33.68 μm, be coated with the coating layer of aluminum diethylphosphinate at the outside surface of core, wherein, the mass ratio of aluminum diethylphosphinate and Calcium hydrogen carbonate is 100:10; The particle diameter D(50 of described cladded type fire retardant) be 50.13 μm; Water ratio is 0.25%; Tap density is 486g/L.
The preparation method of described cladded type fire retardant, comprises the steps:
A) get 105g Calcium hydrogen carbonate to add in 850g water, be made into Calcium hydrogen carbonate suspension;
B) be 10:100 by the mass ratio of Calcium hydrogen carbonate core and aluminum diethylphosphinate coating layer, the aluminum sulfate aqueous solution of 3984g 90% is added in Calcium hydrogen carbonate suspension, in above-mentioned mixing solutions, add the diethyl phospho acid sodium water solution of 5169g 90%, react and complete at 100 DEG C;
C) filtered by coating reaction product, wash, 120 DEG C of dryings, obtain cladded type fire retardant B4.
The EDAX results (characterizing with Conc) of B4 is as follows:
C：33.805 wt%；O：31.008 wt%； Al：8.346 wt%；P：26.457 wt%；Ca：0.384 wt%。
embodiment 5
A kind of cladded type fire retardant, containing particle diameter D(50) be light calcium carbonate, the D(50 of 21.43 μm) be the core of 33.68 μm of Calcium hydrogen carbonate mixtures, the coating layer of aluminum diethylphosphinate is coated with at the outside surface of core, wherein, the mass ratio of light calcium carbonate, Calcium hydrogen carbonate mixture and aluminum diethylphosphinate coating layer is 20:10:100; The particle diameter D(50 of described cladded type fire retardant) be 60.76 μm; Water ratio is 0.42%; Tap density is 610g/L.
The preparation method of described cladded type fire retardant, comprises the steps:
A) get 200g light calcium carbonate and 100g Calcium hydrogen carbonate adds in 1816g water, be made into light calcium carbonate and Calcium hydrogen carbonate suspension;
B) be 20:10:100 by the mass ratio of light calcium carbonate, Calcium hydrogen carbonate mixture core and aluminum diethylphosphinate coating layer, the diethyl phospho acid sodium water solution of the aluminum sulfate aqueous solution of 4269g 20% and 3165g 35% is added in above-mentioned suspension simultaneously, reacts and complete at 0 DEG C;
C) filtered by coating reaction product, wash, 90 DEG C of dryings, obtain cladded type fire retardant B5.
The EDAX results (characterizing with Conc) of B5 is as follows:
C：33.979wt%；O：31.034wt%； Al：8.207wt%；P：26.041wt%；Ca：0.739 wt%。
embodiment 6-embodiment 21
Take high polymers by the weight percent in table 2, fire retardant, processing aid send in twin screw extruder after mixing in high-speed stirring mixer; Glass fibre is added by the side of twin screw extruder system of feeding, and melt extrude through twin screw extruder, cooling, granulation, obtain high polymers composition in a water bath; And measuring its raw smoke which (TSR), heat release amount (THR), UL-94 flame retardant rating, extent of corrosion Δ D and notched Izod impact strength, concrete test data is listed in table 2.The concrete proportioning (wt%) respectively formed in table 2 embodiment 6-21 and test result thereof
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | |
| PBT | 76 | 76 | 76 | |||||
| PA6 | 30 | |||||||
| PA66 | 70 | 50 | 50 | 50 | ||||
| PPE | 21 | |||||||
| HTPA | ||||||||
| Glass fibre 1 | 25 | 25 | 25 | 25 | ||||
| Glass fibre 2 | 30 | |||||||
| Processing aid | 5 | 5 | 5 | 5 | 6 | 6 | 6 | 3 |
| Comparative example 1(A1) | 20 | |||||||
| Comparative example 2(A2) | 18 | |||||||
| Comparative example 3(A3) | 16 | |||||||
| Comparative example 4(A4) | ||||||||
| Comparative example 5(A5) | ||||||||
| Comparative example 6(A6) | 20 | |||||||
| Comparative example 7(A7) | 18 | |||||||
| Embodiment 1(B1) | 20 | |||||||
| Embodiment 2(B2) | 18 | |||||||
| Embodiment 3(B3) | ||||||||
| Embodiment 4(B4) | ||||||||
| Embodiment 5(B5) | ||||||||
| Flame retardant properties (1.5mm) | ncl | V-1 | V-1 | V-1 | V-1 | V-1 | V-1 | V-1 |
| Raw smoke which TSR(m 2/m 2） | 1690 | 3295 | 2642 | 1995 | 2380 | 1959 | 1279 | 2056 |
| Heat release amount THR (MJ/m 2) | 121 | 98 | 88 | 75 | 68 | 63 | 54 | 98 |
| Extent of corrosion Δ D(mm) | 0.42 | 1.68 | 0.95 | 0.64 | 0.61 | 0.48 | 0.11 | 1.80 |
| Notched Izod impact strength (KJ/m 2) | 10.8 | 7.5 | 8.2 | 9.9 | 5.2 | 5.7 | 6.6 | 7.8 |
Continued 2
| Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | Embodiment 21 | |
| PBT | ||||||||
| PA6 | 30 | 30 | 70 | 50 | 50 | |||
| PA66 | ||||||||
| PPE | 21 | 21 | ||||||
| HTPA | 51 | 51 | 51 | |||||
| Glass fibre 1 | 30 | 30 | 30 | |||||
| Glass fibre 2 | 30 | 30 | 25 | 25 | 25 | |||
| Processing aid | 3 | 3 | 5 | 5 | 5 | 2 | 2 | 2 |
| Comparative example 1(A1) | ||||||||
| Comparative example 2(A2) | ||||||||
| Comparative example 3(A3) | ||||||||
| Comparative example 4(A4) | 20 | |||||||
| Comparative example 5(A5) | 17 | |||||||
| Comparative example 6(A6) | ||||||||
| Comparative example 7(A7) | 17 | |||||||
| Embodiment 1(B1) | ||||||||
| Embodiment 2(B2) | 16 | |||||||
| Embodiment 3(B3) | 16 | |||||||
| Embodiment 4(B4) | 20 | |||||||
| Embodiment 5(B5) | 17 | |||||||
| Flame retardant properties (1.5mm) | V-1 | V-1 | ncl | V-0 | V-0 | V-1 | V-1 | V-1 |
| Raw smoke which TSR(m 2/m 2） | 1382 | 1473 | 1570 | 3682 | 2097 | 2825 | 2201 | 1574 |
| Heat release amount THR (MJ/m 2) | 82 | 87 | 113 | 97 | 83 | 133 | 119 | 93 |
| Extent of corrosion Δ D(mm) | 0.79 | 0.88 | 0.45 | 0.94 | 0.67 | 1.75 | 1.02 | 0.63 |
| Notched Izod impact strength (KJ/m 2) | 8.5 | 9.1 | 14.7 | 11.8 | 13.6 | 7.9 | 8.9 | 9.6 |
From upper table 2, cladded type fire retardant of the present invention is applied in high polymers composition, compared to compound flame redundant, can reduce the raw smoke which in fire-retardant polymeric compositions combustion processes and heat release amount to a great extent, little to Screw Corrosion degree.
Secondly, respectively morphologic observation has been carried out to the cladded type fire retardant prepared by light calcium carbonate, aluminum diethylphosphinate and the embodiment of the present invention 2 by scanning electronic microscope, the results are shown in Figure 1, Fig. 4, Fig. 7.As apparent from Fig. 1, Fig. 4 can, light calcium carbonate particle is block crystal formation, smooth surface, soilless sticking trend; Aluminum diethylphosphinate is the bar-shaped close-packed structure of bar.Cladded type flame retardant particle surface shown by Fig. 7 has and is obviously coated with the bar-shaped material of bar, and particle is certain lumphy structure, slightly reunites.
Claims (19)
1. a cladded type fire retardant, is characterized in that, is the core of the carbonate of 1 μm ~ 90 μm, is coated with the coating layer of dialkylphosphinic salts fire retardant at the outside surface of core containing particle diameter; The core particle diameter of described carbonate is preferably 15 μm ~ 50 μm.
2. cladded type fire retardant according to claim 1, is characterized in that, described core and coating layer mass ratio are 1:100 ~ 60:100; Be preferably 10:100 ~ 45:100.
3. cladded type fire retardant according to claim 1 and 2, is characterized in that, the particle diameter of described cladded type fire retardant is 5 μm ~ 150 μm; Be preferably 15 μm ~ 90 μm; Be more preferably 25 μm ~ 70 μm.
4. cladded type fire retardant according to claim 1 and 2, is characterized in that, the water ratio of described cladded type fire retardant is 0.01 wt% ~ 10wt%, is preferably 0.1 wt% ~ 1wt%.
5. cladded type fire retardant according to claim 1 and 2, is characterized in that, the tap density of described cladded type fire retardant is 50 g/L ~ 850g/L, is preferably 200 g/L ~ 650g/L.
6. cladded type fire retardant according to claim 1 and 2, is characterized in that, the solubleness of described cladded type fire retardant in water, organic solvent or water and ORGANIC SOLVENT MIXTURES is 0.005 wt% ~ 9.99wt%.
7. cladded type fire retardant according to claim 1, is characterized in that, described carbonate is selected from one or more mixtures in carbonic acid normal salt, acid carbonate, subcarbonate; Described carbonic acid normal salt is selected from one or more mixtures in magnesiumcarbonate, zinc carbonate, water-ground limestone, light calcium carbonate, is preferably magnesiumcarbonate, light calcium carbonate; Described acid carbonate is selected from one or more mixtures in Magnesium hydrogen carbonate, Calcium hydrogen carbonate, sodium bicarbonate, is preferably Calcium hydrogen carbonate; Described subcarbonate is selected from one or more mixtures in ventilation breather, zinc subcarbonate, magnesium basic carbonate, is preferably zinc subcarbonate.
8. cladded type fire retardant according to claim 1, is characterized in that, described dialkylphosphinic salts fire retardant has such as formula the molecular structure shown in I:
Wherein, R
1, R
2identical or different, be expressed as straight or branched C1-C6 alkyl;
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr or Mn;
M is 2-4.
9. cladded type fire retardant according to claim 8, is characterized in that, described R
1, R
2identical or different, be methyl, ethyl, propyl group, butyl, hexyl; Described M is Mg, Ca, Al, Zn.
10. cladded type fire retardant according to claim 8 or claim 9, it is characterized in that, described dialkylphosphinic salts is selected from one or more mixtures in aluminum diethylphosphinate, dipropyl phospho acid aluminium, dibutyl phospho acid zinc, dihexyl phospho acid magnesium, ethyl-butyl phospho acid calcium; Be preferably aluminum diethylphosphinate.
The preparation method of 11. 1 kinds of cladded type fire retardants as described in any one of claim 1-10, is characterized in that, comprise the steps:
A) carbonate is dispersed in water, makes suspension;
B) the dialkylphosphinic salts aqueous solution, the metallic compound aqueous solution are added in suspension carry out coating reaction;
C) by the filtration of coating reaction product, washing, drying, cladded type fire retardant is obtained.
The preparation method of 12. cladded type fire retardants according to claim 11, it is characterized in that, described dialkylphosphinic salts is selected from one or more mixtures in diethyl phospho acid sodium/potassium, dipropyl phospho acid sodium/potassium, dibutyl phospho acid sodium/potassium, ethyl-butyl phospho acid sodium/potassium, dihexyl phospho acid sodium/potassium; Be preferably diethyl phospho acid sodium.
13. the preparation method of cladded type fire retardant according to claim 11, it is characterized in that, described metallic compound is selected from one or more in the compound of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr or Mn; Be preferably one or more in the compound of Mg, Ca, Al or Zn; Be more preferably the compound of Al.
14. the preparation method of cladded type fire retardant according to claim 11, is characterized in that, described step a), b), c) in, disperse, add, coating reaction, filtration, washing temperature be 0-100 DEG C, dry temperature is 80 DEG C-230 DEG C.
15. cladded type fire retardants according to any one of claim 1-10 are as the purposes of fire retardant.
16. 1 kinds of polymeric compositions comprising the cladded type fire retardant described in any one of claim 1-10.
17. polymeric compositions according to claim 16, is characterized in that, comprise the cladded type fire retardant described in any one of claim 1-10 of 5wt% ~ 25wt%, 45 wt% ~ 80 wt% superpolymer or its mixtures.
18. polymeric compositions according to claim 16 or 17, it is characterized in that, described superpolymer is one or more the mixture in PA, PBT, PET, PPE, TPEE, HTPA; Be preferably one or more mixtures in PA, PBT, PPE, HTPA.
19. polymeric compositions according to claim 16-18, it is characterized in that, described polymeric compositions also comprises the filler of 0 ~ 30wt% and the auxiliary agent of 0 ~ 5wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510340262.7A CN104861206B (en) | 2015-06-18 | 2015-06-18 | A kind of cladded type fire retardant and preparation method and application and the polymeric compositions being made from it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510340262.7A CN104861206B (en) | 2015-06-18 | 2015-06-18 | A kind of cladded type fire retardant and preparation method and application and the polymeric compositions being made from it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104861206A true CN104861206A (en) | 2015-08-26 |
| CN104861206B CN104861206B (en) | 2017-12-29 |
Family
ID=53907419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510340262.7A Expired - Fee Related CN104861206B (en) | 2015-06-18 | 2015-06-18 | A kind of cladded type fire retardant and preparation method and application and the polymeric compositions being made from it |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104861206B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575361A (en) * | 2018-11-23 | 2019-04-05 | 洛阳赛图新材料科技有限公司 | A kind of preparation method of the cladded type fire retardant of excellent electrical properties |
| US11401416B2 (en) | 2017-10-17 | 2022-08-02 | Celanese Sales Germany Gmbh | Flame retardant polyamide composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6420459B1 (en) * | 1999-01-30 | 2002-07-16 | Clariant Gmbh | Flame-retarding thermosetting compositions |
| US20110021676A1 (en) * | 2008-03-03 | 2011-01-27 | Clariant Finance (Bvi) Limited | Method for the Production of a Flame-retardant, Non-corrosive, and Easily flowable Polyamide and Polyester Molding Compounds |
| CN102010618A (en) * | 2010-11-19 | 2011-04-13 | 桐城市信得新材料有限公司 | Method for preparing encapsulated red phosphorus |
| CN103318937A (en) * | 2013-05-22 | 2013-09-25 | 合肥安聚达新材料科技有限公司 | Production method of continuously industrialized metal doped zinc hydroxystannate microencapsulated calcium carbonate |
| CN103509289A (en) * | 2013-09-30 | 2014-01-15 | 广东聚石化学股份有限公司 | Injection molding grade flame retardant PVC/ABS alloy material and preparation method thereof |
-
2015
- 2015-06-18 CN CN201510340262.7A patent/CN104861206B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6420459B1 (en) * | 1999-01-30 | 2002-07-16 | Clariant Gmbh | Flame-retarding thermosetting compositions |
| US20110021676A1 (en) * | 2008-03-03 | 2011-01-27 | Clariant Finance (Bvi) Limited | Method for the Production of a Flame-retardant, Non-corrosive, and Easily flowable Polyamide and Polyester Molding Compounds |
| CN102010618A (en) * | 2010-11-19 | 2011-04-13 | 桐城市信得新材料有限公司 | Method for preparing encapsulated red phosphorus |
| CN103318937A (en) * | 2013-05-22 | 2013-09-25 | 合肥安聚达新材料科技有限公司 | Production method of continuously industrialized metal doped zinc hydroxystannate microencapsulated calcium carbonate |
| CN103509289A (en) * | 2013-09-30 | 2014-01-15 | 广东聚石化学股份有限公司 | Injection molding grade flame retardant PVC/ABS alloy material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11401416B2 (en) | 2017-10-17 | 2022-08-02 | Celanese Sales Germany Gmbh | Flame retardant polyamide composition |
| CN109575361A (en) * | 2018-11-23 | 2019-04-05 | 洛阳赛图新材料科技有限公司 | A kind of preparation method of the cladded type fire retardant of excellent electrical properties |
| CN109575361B (en) * | 2018-11-23 | 2021-06-29 | 洛阳赛图新材料科技有限公司 | Preparation method of coated flame retardant with excellent electrical property |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104861206B (en) | 2017-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6648297B2 (en) | Halogen-free flame retardant reblending system for glass fiber reinforced nylon and its use in halogen free flame retardant glass fiber reinforced nylon materials | |
| CN112225985B (en) | Flame-retardant PP composite material and preparation method thereof | |
| CN101665611B (en) | High tenacity halogen free inflaming retarding ABS resin containing nano level flame retardant and preparation method thereof | |
| CN110054807B (en) | Phosphorus-nitrogen halogen-free flame retardant composition for improving thermal stability by using inorganic metal phosphite and application thereof | |
| CN103627068A (en) | Low-smoke halogen-free high-flame retardation wire cable material and preparation method thereof | |
| CN102477184B (en) | High-glossiness flame-retardant polypropylene composite and preparation method thereof | |
| Zhang et al. | Flammable, thermal, and mechanical properties of intumescent flame retardant PP/LDH nanocomposites with different divalent cations | |
| CN104877177B (en) | A kind of cladded type fire retardant and preparation method and application and the moulding compound being made from it | |
| CN101659779A (en) | Halogen-free flame-retardant ABS resin and preparation method thereof | |
| EP3423522A1 (en) | Flame-retardant polyamide composition | |
| CN106009585A (en) | Halogen-free flame retardation polycarbonate material and preparation method thereof | |
| CN105838067B (en) | Halogen-free fire-retarding reinforced polyamide composition and product prepared therefrom | |
| CN113817263A (en) | Halogen-free flame-retardant polypropylene composition and preparation method and application thereof | |
| Laoutid et al. | Flame‐retardant action of red phosphorus/magnesium oxide and red phosphorus/iron oxide compositions in recycled PET | |
| CN104861206A (en) | Coated flame retardant, preparation method and application thereof, as well as high polymer composition comprising coated flame retardant | |
| CN104861205B (en) | A kind of cladded type fire retardant and preparation method and application and the polymeric compositions being made from it | |
| CN101659778A (en) | Expanded halogen-free flame-retardant ABS compound material | |
| KR20070103884A (en) | Fire prevention coating composition and preparation method thereof | |
| CN105670154A (en) | PVC flame-retardant fire-protection threading pipe | |
| CN103881203A (en) | Low-smoke halogen-free flame-retardant polyethylene composite material and preparation method thereof | |
| CN105801905B (en) | A kind of phosphorus system synergistic flame retardant and its manufacture method and application | |
| CN102532690A (en) | Ceramic-fiber-reinforced flame-retardant modified polypropylene complex and preparation method thereof | |
| CN103819808B (en) | Electric cable material with low smoke and halogen free and radio frequency cable | |
| CN109251526A (en) | Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using alkyl phosphite | |
| CN113604002A (en) | Flame-retardant heat-resistant ABS plastic particle |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190716 Address after: 519050 No. 177, No. 9 Petrochemical Road, Nanshui Town, Jinwan District, Zhuhai City, Guangdong Province Patentee after: Zhuhai Wantong Chemical Co., Ltd. Address before: 510633 Comprehensive Service Building of Guangzhou Science and Technology Innovation Base, No. 80 Lanyue Road, Science City, Guangzhou High-tech Industrial Development Zone, Guangdong Province Patentee before: Guangzhou Kingsky Material Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171229 Termination date: 20200618 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |