CN104861206B - A kind of cladded type fire retardant and preparation method and application and the polymeric compositions being made from it - Google Patents
A kind of cladded type fire retardant and preparation method and application and the polymeric compositions being made from it Download PDFInfo
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Abstract
The invention discloses a kind of cladded type fire retardant, the core containing the carbonate that particle diameter is 1 μm ~ 90 μm, the clad of dialkylphosphinic salts fire retardant is coated with the outer surface of core；The core particle diameter of the carbonate is preferably 15 μm ~ 50 μm.Carbonate is the synergist of dialkylphosphinic salts fire retardant in the cladded type fire retardant of the present invention, and heat release amount is small in the polymeric compositions combustion process added with the cladded type fire retardant, and raw smoke is few, and the extent of corrosion of processing unit (plant) screw rod is reduced.Simultaneously, the cladded type fire retardant realizes the high efficiency composition of dialkylphosphinic salts fire retardant and carbonate, it is uneven to solve the problems, such as that compound flame redundant mixture disperses in resin, the cooperative effect of both components can be farthest played, there is more preferable synergistic effect relative to compound flame redundant mixture.
Description
Technical field
The invention belongs to pluronic polymer field, is related to a kind of cladded type fire retardant, and in particular to dialkylphosphinic salts
Fire retardant is coated on the cladded type fire retardant that the surface of carbonate is formed, and the preparation method of the cladded type fire retardant and application
With the polymeric compositions being made from it.
Background technology
After organic synthesis high polymer material widely uses, the mankind start to face new fire threat, and reason is this
Class material is mostly inflammable or flammable.So adding fire retardant in the material turns into fire preventing, fire is reduced
One of dangerous feasibility and necessity measure.But according to data statistics, death by accident is due to largely poisonous and harmful in fire
Caused by the asphyxia of gas and cigarette, so suppression cigarette, attenuation are mentioned in the same breath with fire-retardant.Gradually substitution has halogen resistance to halogen-free flame retardants
Agent is fired, is widely used in high polymer material, precisely in order on the premise of guarantee is fire-retardant, reaches suppression cigarette, the effect of attenuation.
Dialkylphosphinic salts are as a kind of efficient phosphorus series non-halogen fire retardant, molding combination small with amount of flame-retardant agent
The characteristics of thing good mechanical property, color and luster is good, and smoke density is low, and CTI values are high.Polymeric compositions added with dialkylphosphinic salts
In combustion process, dialkylphosphinic salts can substantially reduce the decomposition temperature of polymeric compositions, promote polymeric compositions to carry
Preceding decomposition, layer of charcoal can be formed at a lower temperature, protect the polymeric compositions under layer of charcoal not drawn at a higher temperature
Combustion, so as to play good flame retardant effect.Successively have studied alkyl phosphinic acid zinc/aluminium/calcium does fire retardant to Ticona companies of the U.S.
Performance in PA and PBT, it is 15% and the addition in PA to draw Methylethyl phosphinic acids aluminium/addition of the calcium in PBT
For 20% when, UL94 V-0 fire-retardant ranks can be reached.Regrettably, because dialkylphosphinic salts are by promoting height
Ionomer compositions resolve into charcoal and reach fire-retardant purpose in advance, in not exclusively combustion when this results in fire-retardant polymeric compositions burning
Burning state, and substantial amounts of cigarette is produced, and substantial amounts of heat is released in the starting stage of burning, add to a certain extent in fire
Death by accident.
In order to solve the problems, such as life cigarette that fire-retardant polymeric compositions imperfect combustion is brought, first technology gives a variety of solutions
Certainly scheme.CN103724967A adds Compositional type auxiliary agent in flame-retarded resin and solves the problems, such as that raw smoke is big, and the Compositional type helps
Agent by following components of intermingling material percentage by weight by being formed：Magnesium hydroxide 0.5wt%-4wt%, Firebrake ZB 1wt%-6wt%, point
Son sieve activation powder 1wt%-5wt%, magnesium hydroxide, Firebrake ZB, molecular sieve activation powder are mixed, stirred, that is, the compounding is made
Type auxiliary agent.CN101591468A is added in resin system：0.2wt%-2wt% compound drop fumicants and 1wt%-6wt% it is low
Smoke accelerator.
Meanwhile when dialkylphosphinic salts are applied to high-temperature nylon or polyester, the mould added with dialkylphosphinic salts
Molding composition can produce heavy corrosion to the metal parts of processing unit (plant) in process.（US 20110021676A1）.
In order to solve the problems, such as that moulding compound corrodes to processing unit (plant) metal parts, patent US 20110021676A1 will
Together with dialkylphosphinic salts and the metal salt of organic acid or inorganic acid compound, applied in nylon or polyester, relative to list
The nylon or polyester of dialkylphosphinic salts are solely used, substantially increases its mobility, and alleviate molding to a certain extent
Corrosion of the composition to processing unit (plant) metal parts.But above-mentioned patent（US 20110021676A1）In compound flame redundant only
It is that various fire retardants are subjected to mechanical-physical mixing in use or prior to use, the problem of scattered uneven is present, and due to having
The metal salt addition of machine acid or inorganic acid is big, poor with material compatibility, can seriously damage moulding compound mechanical performance.
Prior art above is that fire retardant and auxiliary agent are carried out into mechanical-physical mixing in use or prior to use, typically
The problem of scattered uneven all be present, it is impossible to the cooperative effect between each component is played completely, may be to the other sides of polymer
The performance in face impacts.
The content of the invention
The primary and foremost purpose of the present invention is to provide a kind of cladded type resistance of dialkylphosphinic salts fire retardant cladding carbonate
Agent is fired, when the cladded type fire retardant is applied to high polymer composition, can largely reduce fire-retardant high polymer combination
Life smoke and heat release amount in thing combustion process.Meanwhile the cladded type fire retardant realize dialkylphosphinic salts fire retardant with
The high efficiency composition of carbonate, compound flame redundant can be efficiently solved and disperse the problem of uneven, improve fire-retardant polymeric compositions
The homogeneity of performance.And when the cladded type fire retardant is applied to high polymer composition, it can largely mitigate height
To the corrosion of processing unit (plant) screw rod in polymer composition process.
It is a further object of the present invention 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 for including above-mentioned cladded type fire retardant.
The present invention is achieved by the following technical solutions：
A kind of cladded type fire retardant, the core containing the carbonate that particle diameter is 1 μm ~ 90 μm, is coated in the outer surface of core
There is the clad of dialkylphosphinic salts fire retardant；The core particle diameter of the carbonate is preferably 15 μm ~ 50 μm.
The core is 1 with clad mass ratio：100~60：100.Preferably, the core is with clad mass ratio
10：100~45：100.The cladded type fire retardant of core and clad mass ratio described in non-invention, is combined applied to high polymer
During thing, heat release amount is big in combustion process, and raw smoke is more, big to the extent of corrosion of processing unit (plant) screw rod.
Wherein, the particle diameter of the cladded type fire retardant is 5 μm ~ 150 μm；Preferably 15 μm ~ 90 μm；More preferably 25 μm
~70μm。
Wherein, the moisture content of the cladded type fire retardant is 0.01 wt% ~ 10wt%, preferably 0.1 wt% ~ 1wt%.
Wherein, the bulk density of the cladded type fire retardant is 50 g/L ~ 850g/L, preferably 200 g/L ~ 650g/
L。
Wherein, solubility of the cladded type fire retardant in water, organic solvent or water and ORGANIC SOLVENT MIXTURES is
0.005wt%~9.99wt%。
Wherein, the organic solvent is alcohol, ether, ketone, carboxylic acid, ester, aliphatic hydrocarbon, alicyclic nytron
One or more mixtures in thing, aromatic hydrocarbons, halogenated hydrocarbons.Preferably methanol, ethanol, ethylene glycol, ether,
One or more in glycol ether, acetone, acetic acid, ethyl acetate, n-hexane, benzene, toluene, hexamethylene, chloroform, carbon tetrachloride
Mixture.
Wherein, one or more mixing of the carbonate in carbonic acid normal salt, acid carbonate, subcarbonate
Thing；One or more mixtures of the carbonic acid normal salt in magnesium carbonate, zinc carbonate, powdered whiting, precipitated calcium carbonate, it is excellent
Elect magnesium carbonate, precipitated calcium carbonate as；One kind in magnesium bicarbonate, calcium bicarbonate, sodium acid carbonate of the acid carbonate or
A variety of mixtures, preferably calcium bicarbonate；The subcarbonate is selected from basic copper carbonate, basic zinc carbonate, basic magnesium carbonate
In one or more mixtures, preferably basic zinc carbonate.
Wherein, the dialkylphosphinic salts fire retardant has molecular structure shown in formula I：
Wherein, R1, R2It is identical or different, it is 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, the R1, R2It is identical or different, it is methyl, ethyl, propyl group, butyl, hexyl.
Preferably, the M is Mg, Ca, Al, Zn.
It is highly preferred that the dialkylphosphinic salts are selected from aluminum diethylphosphinate, dipropyl phosphinic acids aluminium, dibutyl time
One or more mixtures in zinc phosphonate, dihexyl phosphinic acids magnesium, ethyl-butyl phosphinic acids calcium；Preferably diethyl phosphinic acids
Aluminium.
A kind of preparation method of above-mentioned cladded type fire retardant, comprises the following steps：
a）Carbonate is dispersed in water, suspension is made；
b）The dialkylphosphinic salts aqueous solution, the metallic compound aqueous solution are added in suspension and carry out coating reaction；
c）By the filtering of coating reaction product, washing, dry, obtain cladded type fire retardant.
Wherein, the coating reaction refers to that the dialkylphosphinic salts aqueous solution and the generation of metallic compound reactant aqueous solution are heavy
Form sediment, the precipitation generated is attached to the surface of carbonate core, forms coating reaction product.
Wherein, the dialkyl phosphinic acid/salt is diethyl phosphinic acids sodium/potassium, dipropyl phosphinic acids sodium/potassium, dibutyl
One or more mixtures in phosphinic acids sodium/potassium, ethyl-butyl phosphinic acids sodium/potassium, dihexyl phosphinic acids sodium/potassium；Preferably
Diethyl phosphinic acids sodium.
Wherein, the metallic compound is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr or Mn change
One or more in compound；One or more preferably in Mg, Ca, Al or Zn compound；More preferably Al chemical combination
Thing.
Wherein, described step a）、b）、c）In, disperse, add, reacting, filtering, the temperature of washing is 0-100 DEG C, dry
Dry temperature is 80 DEG C -230 DEG C.
The invention also discloses purposes of the above-mentioned cladded type fire retardant as fire retardant.
The invention also discloses the polymeric compositions for including above-mentioned cladded type fire retardant.Wherein, the high polymer combination
Thing includes the wt% cladded type fire retardants of 5 wt% ~ 25, the wt% high polymers of 45 wt% ~ 80 or its mixture.
Wherein, the high polymer is one or more mixtures in PA, PBT, PET, PPE, TPEE, HTPA；It is preferred that
For one or more mixtures in PA, PBT, PPE, HTPA.
Wherein, the polymeric compositions, 0 ~ 30 wt% glass fibre can according to the demand of material different performance, be added
Or filler and 0 ~ 5wt% auxiliary agent.
The filler of the present invention is commonly used to strengthen or the material of filled polymer, it is possible to use two or more are inorganic to fill out
The mixture of material and/or reinforcing agent.Filler can include following one or more：Glass fibre, glass flake, kaolin,
Clay, talcum powder, wollastonite, calcium carbonate, silica, carbon fiber, potassium titanate etc..
The processing aid can not disturb the foregoing additional component wished property and still improve other beneficial properties, such as
Antioxidant, lubricant, releasing agent, nucleator, toner, light stabilizer.
The present invention compared with prior art, has the advantages that：
1）The cladded type fire retardant of the present invention, carbonate core surfaces are coated on using dialkylphosphinic salts as shell,
During applied to high polymer composition, the life cigarette during fire-retardant high polymer composition burn can be largely reduced
Amount and heat release amount.
2）When the cladded type fire retardant of the present invention is applied to high polymer composition, can largely it mitigate high poly-
To the corrosion of processing unit (plant) screw rod in polymer composition process.
3）Dialkylphosphinic salts are coated on carbonate builders surface, realize two by the cladded type fire retardant of the present invention
The high efficiency composition of alkyl phosphinate and carbonate, compound flame redundant can be efficiently solved and disperseed the problem of uneven, improve resistance
The homogeneity of polymeric compositions performance is fired, reduces the influence to polymer composition other performance.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph of precipitated calcium carbonate.
Fig. 2 is the energy spectrum diagram of precipitated calcium carbonate.
Fig. 3 is the constituent content table in precipitated calcium carbonate energy spectrum diagram.
Fig. 4 is the electron scanning micrograph of aluminum diethylphosphinate.
Fig. 5 is the energy spectrum diagram of aluminum diethylphosphinate.
Fig. 6 is the constituent content table in aluminum diethylphosphinate energy spectrum diagram.
Fig. 7 is the electron scanning micrograph of the cladded type fire retardant prepared by the embodiment of the present invention 2.
Fig. 8 is the energy spectrum diagram of the cladded type fire retardant prepared by the embodiment of the present invention 2.
Fig. 9 is the constituent content table in the cladded type fire retardant energy spectrum diagram prepared by the embodiment of the present invention 2.
Embodiment
The present invention is further illustrated below by embodiment, following examples are the preferable embodiment party of the present invention
Formula, but embodiments of the present invention are not limited by following embodiments.The person skilled in the art in the field is according to above-mentioned hair
Bright content, the modifications and adaptations of some non-intrinsically safes made for the present invention still fall within protection scope of the present invention.
Now raw material selected in embodiment and comparative example are done as described below, but be not limited to these materials：
PBT：PBT 1100-211M（Taiwan Changchun group）
PA66：PA66 EP-158（Hua Feng groups）
PA6：PA6 M2000（Meida Nylon Co., Ltd., Xinhui, Guangdong）
PPE：PPE 100Z（Japanese Asahi Chemical Industry）
HTPA：Amodel® A-6000（Solvay）
Glass fibre 1：ECS13-4.5-534（Megalith group）
Glass fibre 2：ECS301-HP（Chongqing Polycomp International Co., Ltd）；
Antioxidant：1010,（Jin Haiyabao）Antioxidant：168（Jin Haiyabao）
Lubricant：GLYCOLUBE-P（Nanjing close friend's auxiliary agent Chemical Co., Ltd.）
Releasing agent：Silicone master batch（Dow Corning）
Nucleator：Sarin（DUPONT）
Light stabilizer：770（Ciba Specialty Chemicals）
The method that the present invention characterizes cladded type fire retardant pattern is ESEM（SEM）.
The method of present invention analysis cladded type fire retardant surface composition is power spectrum（EDS）.
Present invention power spectrum（EDS）Analyze cladded type fire retardant surface composition, concrete operations：By the SEM scanning areas of sample
Domain is extended to 5000 times, and area S=100 μm in SEM figures are scanned using EDS2Sample in region, obtain the surface area sample
The energy spectrum diagram of surface composition.Element existing for spectral peak representative in energy spectrum diagram, the atomic mass percentage of element represent composition sample
The concentration of each element of material.
The method of testing of cladded type fire retardant and core particle diameter of the present invention is as follows：
Utilize the particle diameter distribution of the scattered cladded type fire retardant and core in the liquid phase of laser particle analyzer test.Specific behaviour
As：According to the particle size of cladded type fire retardant and core, 0.05g ~ 1.0g samples are taken in beaker, add alcohol and water
Mixed solution is dispersed with stirring, and is poured into laser particle analyzer, after about 1min, you can measures the particle diameter of cladded type fire retardant and core
Distribution.The D that the particle size of cladded type fire retardant and core of the present invention is measured with laser particle analyzer（50）As evaluation
Foundation.
Cladded type fire retardant bulk density method of testing of the present invention is with reference to GB20316.2-《The measure of bulk density》
Measure.
The method of testing reference GBT 6284-2006 of cladded type fire retardant moisture content of the present invention-《In chemical products
The universal method loss on drying of determination of moisture》Measure.
The method of testing of cladded type fire retardant solubility of the present invention is balancing method.Concrete operations are：25 DEG C, it will coat
Type fire retardant is added in solution, constant temperature stirring certain time, and the composition for standing post analysis upper solution is molten as at this temperature
Xie Du.
The solution refers in water, organic solvent or water and ORGANIC SOLVENT MIXTURES.
Life smoke in the present invention during high polymer composition burn（TSR）With heat release amount（THR）Pass through taper amount
Hot instrument measure.Specific testing standard and sample parameters are as follows：
Testing standard：GB16172-2007-T.
Test parameter：Sample size：100mm x 100mm x 6mm；Radiant cone power 50kW/m2。
TSR numerical value is bigger, shows that raw smoke is bigger in polymeric compositions combustion process；THR numerical value is bigger, shows high poly-
Heat release amount is more in compositions combustion process.
TSR in the present invention in non-glass fibre enhancing PBT polymeric compositions combustion processes is 800 m2/m2~1500m2/m2；
THR is 50 MJ/m2~58MJ/m2。
TSR in the present invention in 25% glass fiber reinforced PA66 polymeric compositions combustion process is 1600 m2/m2~2200m2/
m2；THR is 72 MJ/m2~82MJ/m2。
TSR in the present invention in 30% fiberglass reinforced PA 6/PPE alloy polymeric compositions combustion processes is 1100m2/m2~
1600m2/m2；THR is 80 MJ/m2~90MJ/m2。
TSR in the present invention in the polymeric compositions thing combustion process of 25% fiberglass reinforced PA 6 is 1400m2/m2~2100m2/
m2；THR is 80 MJ/m2~90MJ/m2。
TSR in the present invention in 30% fiberglass reinforced HTPA polymeric compositions combustion processes is 1300m2/m2~1800m2/
m2；THR is 89 MJ/m2~97MJ/m2。
Corrosion Basis Screw Corrosion degree of the present invention evaluation polymeric compositions to processing unit (plant) screw rod（ΔD）It is determined that.
Δ D assay method is as follows：
When compounding combination unit often processes 100t fire-retardant polymeric compositions, same position screw rod is straight before and after measure production
Footpath（DBeforeAnd DAfterwards）, after calculating the production fire-retardant polymeric compositions of 100t, difference DELTA D=D of screw diameterBefore-DAfterwards, Δ D values are bigger,
Represent that Screw Corrosion is more serious.
Non-glass fibre enhancing PBT polymeric compositions are to the Screw Corrosion degree Δ D of compounding combination unit in the present invention
0.05~0.25mm。
25% glass fiber reinforced PA66 polymeric compositions are to the Screw Corrosion degree Δ D of compounding combination unit in the present invention
0.38mm ~0.70mm。
Screw Corrosion journey of the 30% fiberglass reinforced PA 6/PPE alloys polymeric compositions to compounding combination unit in the present invention
It is 0.60 mm ~ 1.05mm to spend Δ D.
The polymeric compositions of 25% fiberglass reinforced PA 6 are to the Screw Corrosion degree Δ D of compounding combination unit in the present invention
0.40mm~0.75mm。
30% fiberglass reinforced HTPA polymeric compositions are to the Screw Corrosion degree Δ D of compounding combination unit in the present invention
0.50mm ~0.80mm。
Notch impact strength：GB 1843-2008.
Combustibility：UL94 Plastics Combustion performance tests；
The test sample measure burning grades of UL 94 for the test sample from every kind of mixture using thickness 1.5mm.
The burning grade as defined in UL 94 below：
V-0：After batten leaves flame, the sustained combustion time is no longer than 10s, and 5 battens amount to 10 times to be continued when lighting
Burning time summation is no more than 50s, no molten drop drippage, flame without spreading to fixture phenomenon, sample light terminate after more than
Brightness burning time is no longer than 30s.
V-1：After batten leaves flame, the sustained combustion time is no longer than 30s, and 5 battens amount to 10 times to be continued when lighting
Burning time summation is no more than 250s, and sample is no longer than 60s lighting the twilight sunset burning time after terminating, other standards as
V-0。
V-2：After batten leaves flame, during sustained combustion, there is molten drop, and molten drop can ignite absorbent cotton indicant,
Other same V-1 of standard.
Unclassified（ncl）：It is unsatisfactory for the grade V-2 that burns.
Comparative example 1- comparative examples 5
Aluminum diethylphosphinate, carbonate are weighed by the percentage by weight in table 1, and system is uniformly mixed in premixing machine
Obtain compound flame redundant A1-A5.
Table 1 comparative example 1-5 (A1-A5) compound flame redundant constituent component mass ratio
Comparative example 6
A kind of cladded type fire retardant, contains particle diameter D（50）For the core of 15.37 μm of magnesium carbonate, in the outer surface of core
The clad of aluminum diethylphosphinate is coated with, wherein, the mass ratio of aluminum diethylphosphinate and magnesium carbonate is 100：0.5；Institute
State the particle diameter D of cladded type fire retardant（50）For 29.87 μm；Moisture content is 0.14%；Bulk density is 552g/L.
The preparation method of the cladded type fire retardant, comprises the following steps：
a）Take 5g magnesium carbonate to add in 995g water, be made into magnesium carbonate suspension；
b）It is 0.5 by the mass ratio of magnesium carbonate core and aluminum diethylphosphinate clad：100, by the two of 2769g 40%
Ethylphosphinic acid sodium water solution is added in magnesium carbonate suspension, and 1422g 60% aluminum sulfate water is added into above-mentioned mixed solution
Solution, react and completed at 80 DEG C；
c）By the filtering of coating reaction product, washing, 80 DEG C of dryings, cladded type fire retardant A6 is obtained.
A6 EDAX results（Characterized with Conc）It 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, contains particle diameter D（50）For the core of 21.43 μm of precipitated calcium carbonate, in the outer of core
Surface coating has the clad of aluminum diethylphosphinate, wherein, the mass ratio of aluminum diethylphosphinate and precipitated calcium carbonate is
100：65；The particle diameter D of the cladded type fire retardant（50）For 33.56 μm；Moisture content is 0.21%；Bulk density is 710g/L.
The preparation method of the cladded type fire retardant, comprises the following steps：
a）Take 125g precipitated calcium carbonates to add in 125g water, be made into precipitated calcium carbonate suspension；
b）It is 65 by the mass ratio of precipitated calcium carbonate core and aluminum diethylphosphinate clad：100, by 615g's 30%
Diethyl phosphinic acids sodium water solution is added in precipitated calcium carbonate suspension, and 771g 20% sulfuric acid is added into above-mentioned mixed solution
Aluminum water solution, react and completed at 95 DEG C；
c）By the filtering of coating reaction product, washing, 230 DEG C of dryings, cladded type fire retardant A7 is obtained.
A7 EDAX results（Characterized with Conc）It 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, contains D（50）For the core of 15.37 μm of magnesium carbonate, coated in the outer surface of core
There is the clad of aluminum diethylphosphinate, wherein, the mass ratio of aluminum diethylphosphinate and magnesium carbonate is 100：1；The cladding
The particle diameter D of type fire retardant（50）For 30.88 μm；Moisture content is 0.11%；Bulk density is 565g/L.
The preparation method of the cladded type fire retardant, comprises the following steps：
a）Take 10g magnesium carbonate to add in 990g water, be made into magnesium carbonate suspension；
b）It is 1 by the mass ratio of magnesium carbonate core and aluminum diethylphosphinate clad：100, by 3692g 30% diethyl
Base phosphinic acids sodium water solution is added in magnesium carbonate suspension, and the aluminum sulfate that 1707g 50% is added into above-mentioned mixed solution is water-soluble
Liquid, react and completed at 70 DEG C；
c）By the filtering of coating reaction product, washing, 150 DEG C of dryings, cladded type fire retardant B1 is obtained.
B1 EDAX results（Characterized with Conc）It 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, contains particle diameter D（50）For the core of 21.43 μm of precipitated calcium carbonate, in the outer of core
Surface coating has the clad of aluminum diethylphosphinate, wherein, the mass ratio of aluminum diethylphosphinate and precipitated calcium carbonate is
100：60；The particle diameter D of the cladded type fire retardant（50）For 30.12 μm；Moisture content is 0.15%；Bulk density is 558g/L.
The preparation method of the cladded type fire retardant, comprises the following steps：
a）Take 100g precipitated calcium carbonates to add in 100g water, be made into precipitated calcium carbonate suspension；
b）It is 60 by the mass ratio of precipitated calcium carbonate core and aluminum diethylphosphinate clad：100, by 369g's 50%
Diethyl phosphinic acids sodium water solution is added in precipitated calcium carbonate suspension, and 1542g 10% sulphur is added into above-mentioned mixed solution
Sour aluminum water solution, react and completed at 60 DEG C；
c）By the filtering of coating reaction product, washing, dry, obtain cladded type fire retardant B2.
B2 EDAX results（Characterized with Conc）It 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, contains particle diameter D（50）For 18.43 μm of basic zinc carbonate, D（50）For 15.87 μm
The core of carbonic acid magnesium compound, the clad of aluminum diethylphosphinate is coated with the outer surface of core, wherein, basic carbonate
The mass ratio of zinc, carbonic acid magnesium compound and aluminum diethylphosphinate clad is 5：40：100；The grain of the cladded type fire retardant
Footpath D（50）For 40.66 μm；Moisture content is 0.35%；Bulk density is 589g/L.
The preparation method of the cladded type fire retardant, comprises the following steps：
a）Take 11.1g basic zinc carbonates and 88.9g magnesium carbonate to add in 500g water, be made into basic zinc carbonate and magnesium carbonate hangs
Supernatant liquid；
b）Mass ratio by basic zinc carbonate, carbonic acid magnesium compound core and aluminum diethylphosphinate clad is 5：40：
100,886g 50% diethyl phosphinic acids sodium water solution is added in calcium carbonate and magnesium carbonate suspension, to above-mentioned mixed solution
Middle addition 1138g 30% aluminum sulfate aqueous solution, reacts and is completed at 100 DEG C；
c）By the filtering of coating reaction product, washing, 200 DEG C of dryings, cladded type fire retardant B3 is obtained.
B3 EDAX results（Characterized with Conc）It 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, contains D（50）For the core of 33.68 μm of calcium bicarbonate, in the appearance bread of core
The clad of aluminum diethylphosphinate is covered with, wherein, the mass ratio of aluminum diethylphosphinate and calcium bicarbonate is 100：10；It is described
The particle diameter D of cladded type fire retardant（50）For 50.13 μm；Moisture content is 0.25%；Bulk density is 486g/L.
The preparation method of the cladded type fire retardant, comprises the following steps：
a）Take 105g calcium bicarbonates to add in 850g water, be made into calcium bicarbonate suspension；
b）It is 10 by the mass ratio of calcium bicarbonate core and aluminum diethylphosphinate clad：100, by 3984g's 90%
Aluminum sulfate aqueous solution is added in calcium bicarbonate suspension, and 5169g 90% diethyl phosphinic acids are added into above-mentioned mixed solution
Sodium water solution, react and completed at 100 DEG C；
c）By the filtering of coating reaction product, washing, 120 DEG C of dryings, cladded type fire retardant B4 is obtained.
B4 EDAX results（Characterized with Conc）It 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, contains particle diameter D（50）For 21.43 μm of precipitated calcium carbonate, D（50）For 33.68 μm of carbon
The core of sour hydrogen calcium compound, the clad of aluminum diethylphosphinate is coated with the outer surface of core, wherein, lightweight carbonic acid
The mass ratio of calcium, calcium bicarbonate mixture and aluminum diethylphosphinate clad is 20：10：100；The cladded type fire retardant
Particle diameter D（50）For 60.76 μm；Moisture content is 0.42%；Bulk density is 610g/L.
The preparation method of the cladded type fire retardant, comprises the following steps：
a）Take 200g precipitated calcium carbonates and 100g calcium bicarbonates to add in 1816g water, be made into precipitated calcium carbonate and bicarbonate
Calcium suspension；
b）Mass ratio by precipitated calcium carbonate, calcium bicarbonate mixture core and aluminum diethylphosphinate clad is 20：
10：100,4269g 20% aluminum sulfate aqueous solution and 3165g 35% diethyl phosphinic acids sodium water solution are added simultaneously above-mentioned
In suspension, react and completed at 0 DEG C；
c）By the filtering of coating reaction product, washing, 90 DEG C of dryings, cladded type fire retardant B5 is obtained.
B5 EDAX results（Characterized with Conc）It is as follows：
C：33.979wt%；O：31.034wt%； Al：8.207wt%；P：26.041wt%；Ca：0.739 wt%.
Embodiment 6- embodiments 21
High polymer, fire retardant, processing aid are weighed by the percentage by weight in table 2 to mix in high-speed stirred batch mixer
It is sent into after uniformly in double screw extruder；Glass fibre is fed system by the side of double screw extruder and added, through twin-screw extrusion
Machine melting extrusion, cool down, be granulated in a water bath, produce high polymer composition；And determine it and give birth to smoke（TSR）, heat release amount
（THR）, UL-94 flame retardant ratings, extent of corrosion Δ D and notch impact strength, specific test data be listed in Table 2 below.
The specific proportioning respectively formed in the embodiment 6-21 of table 2（wt%）And its test result
| 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） | ||||||||
| Fire resistance（1.5mm） | ncl | V-1 | V-1 | V-1 | V-1 | V-1 | V-1 | V-1 |
| Raw smoke TSR（m2/m2） | 1690 | 3295 | 2642 | 1995 | 2380 | 1959 | 1279 | 2056 |
| Heat release amount THR (MJ/m2) | 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 |
| Notch impact strength (KJ/m2) | 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 | |||||||
| Fire resistance（1.5mm） | V-1 | V-1 | ncl | V-0 | V-0 | V-1 | V-1 | V-1 |
| Raw smoke TSR（m2/m2） | 1382 | 1473 | 1570 | 3682 | 2097 | 2825 | 2201 | 1574 |
| Heat release amount THR (MJ/m2) | 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 |
| Notch impact strength (KJ/m2) | 8.5 | 9.1 | 14.7 | 11.8 | 13.6 | 7.9 | 8.9 | 9.6 |
It was found from upper table 2, cladded type fire retardant of the invention is applied in high polymer composition, is hindered compared to Compositional type
Agent is fired, can largely reduce the life smoke and heat release amount in fire-retardant polymeric compositions combustion process, it is rotten to screw rod
Degree of corrosion is small.
Secondly, with SEM respectively to precipitated calcium carbonate, aluminum diethylphosphinate and the institute of the embodiment of the present invention 2
The cladded type fire retardant of preparation has carried out morphologic observation, as a result sees Fig. 1, Fig. 4, Fig. 7.From Fig. 1, Fig. 4, it is apparent that lightweight
Calcium carbonate particle is in block crystal formation, and surface is smooth, soilless sticking trend；Aluminum diethylphosphinate is the bar-shaped close-packed structure of bar.
Cladded type flame retardant particle surface shown by Fig. 7, which has, is substantially coated with the bar-shaped material of bar, and particle is in certain bulk
Structure, it is slight to reunite.
Claims (33)
- A kind of 1. cladded type fire retardant, it is characterised in that the core containing the carbonate that particle diameter is 1 μm ~ 90 μm, in the outer of core Surface coating has the clad of dialkylphosphinic salts fire retardant；The core is 1 with clad mass ratio：100~60：100.
- 2. cladded type fire retardant according to claim 1, it is characterised in that the core particle diameter of the carbonate be 15 μm ~ 50μm。
- 3. cladded type fire retardant according to claim 1, it is characterised in that the core is 10 with clad mass ratio： 100~45：100.
- 4. according to the cladded type fire retardant described in claim any one of 1-3, it is characterised in that the grain of the cladded type fire retardant Footpath is 5 μm ~ 150 μm.
- 5. cladded type fire retardant according to claim 4, it is characterised in that the particle diameter of the cladded type fire retardant is 15 μm ~90μm。
- 6. cladded type fire retardant according to claim 5, it is characterised in that the particle diameter of the cladded type fire retardant is 25 μm ~70μm。
- 7. according to the cladded type fire retardant described in claim any one of 1-3, it is characterised in that the cladded type fire retardant contains Water rate is 0.01 wt% ~ 10wt%.
- 8. cladded type fire retardant according to claim 7, it is characterised in that the moisture content of the cladded type fire retardant is 0.1 wt%~1wt%。
- 9. according to the cladded type fire retardant described in claim any one of 1-3, it is characterised in that the heap of the cladded type fire retardant Product density is 50 g/L ~ 850g/L.
- 10. cladded type fire retardant according to claim 9, it is characterised in that the bulk density of the cladded type fire retardant For 200 g/L ~ 650g/L.
- 11. according to the cladded type fire retardant described in claim any one of 1-3, it is characterised in that the cladded type fire retardant exists Solubility in water, organic solvent or water and ORGANIC SOLVENT MIXTURES is 0.005 wt% ~ 9.99wt%.
- 12. cladded type fire retardant according to claim 1, it is characterised in that the carbonate is selected from carbonic acid normal salt, acid One or more mixtures in carbonate, subcarbonate；The carbonic acid normal salt is selected from magnesium carbonate, zinc carbonate, heavy carbonic acid One or more mixtures in calcium, precipitated calcium carbonate；The acid carbonate is selected from magnesium bicarbonate, calcium bicarbonate, bicarbonate One or more mixtures in sodium；The subcarbonate is in basic copper carbonate, basic zinc carbonate, basic magnesium carbonate One or more mixtures.
- 13. cladded type fire retardant according to claim 12, it is characterised in that the carbonic acid normal salt is magnesium carbonate, lightweight Calcium carbonate.
- 14. cladded type fire retardant according to claim 12, it is characterised in that the acid carbonate is calcium bicarbonate.
- 15. cladded type fire retardant according to claim 12, it is characterised in that the subcarbonate is basic carbonate Zinc.
- 16. cladded type fire retardant according to claim 1, it is characterised in that the dialkylphosphinic salts fire retardant tool There is molecular structure shown in formula I：Wherein, R1, R2It is identical or different, it is 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.
- 17. cladded type fire retardant according to claim 16, it is characterised in that the R1, R2It is identical or different, be methyl, Ethyl, propyl group, butyl, hexyl；The M is Mg, Ca, Al, Zn.
- 18. the cladded type fire retardant according to claim 16 or 17, it is characterised in that the dialkylphosphinic salts are selected from Aluminum diethylphosphinate, dipropyl phosphinic acids aluminium, dibutyl phosphinic acids zinc, dihexyl phosphinic acids magnesium, ethyl-butyl phosphinic acids calcium In one or more mixtures.
- 19. cladded type fire retardant according to claim 18, it is characterised in that the dialkylphosphinic salts are diethyl Phosphinic acids aluminium.
- 20. the preparation method of a kind of cladded type fire retardant as described in claim any one of 1-19, it is characterised in that including such as Lower step：a）Carbonate is dispersed in water, suspension is made；b）The dialkylphosphinic salts aqueous solution, the metallic compound aqueous solution are added in suspension and carry out coating reaction；c）By the filtering of coating reaction product, washing, dry, obtain cladded type fire retardant.
- 21. the preparation method of cladded type fire retardant according to claim 20, it is characterised in that the dialkyl phosphinic acid Salt be selected from diethyl phosphinic acids sodium/potassium, dipropyl phosphinic acids sodium/potassium, dibutyl phosphinic acids sodium/potassium, ethyl-butyl phosphinic acids sodium/ One or more mixtures in potassium, dihexyl phosphinic acids sodium/potassium.
- 22. cladded type fire retardant according to claim 21, it is characterised in that the dialkylphosphinic salts are diethyl Phosphinic acids sodium.
- 23. the preparation method of cladded type fire retardant according to claim 20, it is characterised in that the metallic compound choosing One or more from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr or Mn compound.
- 24. the preparation method of cladded type fire retardant according to claim 23, it is characterised in that the metallic compound is One or more in Mg, Ca, Al or Zn compound.
- 25. the preparation method of cladded type fire retardant according to claim 24, it is characterised in that the metallic compound is Al compound.
- 26. the preparation method of cladded type fire retardant according to claim 20, it is characterised in that described step a）、b）、 c）In, scattered, additions, coating reaction, filtering, the temperature of washing are 0-100 DEG C, the temperature of drying is 80 DEG C -230 DEG C.
- 27. purposes of the cladded type fire retardant according to claim any one of 1-19 as fire retardant.
- A kind of 28. polymeric compositions of the cladded type fire retardant comprising described in claim any one of 1-19.
- 29. polymeric compositions according to claim 28, it is characterised in that the claim 1- comprising 5wt% ~ 25wt% Cladded type fire retardant described in 19 any one, the wt% high polymers of 45 wt% ~ 80 or its mixture.
- 30. the polymeric compositions according to claim 28 or 29, it is characterised in that the high polymer be PA, PBT, One or more mixtures in PET, PPE, TPEE, HTPA.
- 31. polymeric compositions according to claim 30, it is characterised in that the high polymer be PA, PBT, PPE, One or more mixtures in HTPA.
- 32. according to the polymeric compositions described in any one of claim 28,29,31, it is characterised in that the high polymer combination The auxiliary agent of filler and 0 ~ 5wt% of the thing also including 0 ~ 30wt%.
- 33. polymeric compositions according to claim 30, it is characterised in that the polymeric compositions also include 0 ~ 30wt% filler and 0 ~ 5wt% auxiliary agent.
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| US6420459B1 (en) * | 1999-01-30 | 2002-07-16 | Clariant Gmbh | Flame-retarding thermosetting compositions |
| 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 |
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| US6420459B1 (en) * | 1999-01-30 | 2002-07-16 | Clariant Gmbh | Flame-retarding thermosetting compositions |
| 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 |
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