CN110483898A - A kind of resistance to precipitation halogen-free flame retardants of high fluidity and its preparation method and application - Google Patents
A kind of resistance to precipitation halogen-free flame retardants of high fluidity and its preparation method and application Download PDFInfo
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The present invention relates to a kind of high fluidity halogen-free flame retardants of resistance to precipitation, raw material includes the component of following weight percentage: piperazine phosphate 45~70%；Melamine and derivative 20~50%；Inorganic metal zinc compound 5~10%；Surface treating agent 0.1~1.5%；Wherein, the surface treating agent includes lubricant and silicone oil substance, and the mass ratio of the lubricant and silicone oil substance is 0.5~1.2；The silicone oil substance forms cyst wall outside the bulk powder of halogen-free flame retardants.Compared with prior art, the present invention has many advantages, such as that hydrophobicity is good, good fluidity, good flame resistance, solves the problems, such as the bridge formation in fire retardant powder reuniting, agglomeration and process.
Description
Technical field
The present invention relates to the fire retardant combinations of synthetic resin, hinder more particularly, to a kind of resistance to precipitation Halogen of high fluidity
Fire agent and its preparation method and application.
Background technique
Polypropylene (PP) is a kind of thermoplastic resin of function admirable, has chemical resistance, electrical insulating property, high-strength mechanical
Performance and high abrasion processing performance etc. are widely used in the fields such as electronic apparatus, automobile, machinery.However the oxygen of polypropylene material
Index only has 18%, is easy burning and causes fire, the requirement in particular with household electrical appliances and automobile industry to fire-retardant fireproof grade is got over
Come stringenter, develops before new and effective, low smoke and zero halogen, the Flame Retardant Agent of Polypropylene haveing excellent performance and product have good market
Scape.
Currently, the halogen-free flame retardants for polypropylene material is mainly the expansion type phosphor nitrogen system of ammonium polyphosphate (APP) compounding
Fire retardant, APP have many advantages, such as preferable chemical stability, dispersibility, hypotoxicity, but there is also thermal stability that low, moisture absorption is moved
It moves, the defect of poor water resistance, causes APP compound system fire-retardant product in UL746C (70 DEG C ﹡ 168h) immersion test and GB/T
2423.50-2012 humidity is 85%, temperature is 85 DEG C, in the test of the steady damp heat of time 168h, and product surface exists apparent
White powder migration, influences apparent and flame retardant property, limits APP anti-flaming polypropylene material and require stringent family in application environment
Application in the modified plastic industries such as electricity, automobile, new energy battery case.In recent years, although existing patent CN109554930A,
CN103709445A, CN101492881B, which are disclosed, changes APP progress surface using silicone couplet, melamine resin, epoxy resin etc.
Property and microcapsule coated improve water resistance, but are not fully solved the moisture absorption migration problem of APP in the material yet.
Piperazine phosphate is new and effective flame-retardant system fast-developing in recent years, has preferable flame retardant property and at charcoal
Performance, lower water solubility will not cause the moisture absorption and migration in resin, more and more fire-retardant for PP.But piperazine phosphorus
Silicate system also faces some problems in the application: (1) smashed powder is easy to reunite there are biggish charge effect, In
Bad dispersibility in resin is especially easy to influence appearance there are white point in black products；(2) mobility of powder is poor,
It is easy the presence of bridge formation and broken strip in squeezing out blanking process, influences processing performance, reduce production efficiency；It is (3) although water-soluble low,
But powder stacks meeting moisture absorption agglomeration for a long time, compounds non-breakable in process, the residual biggish particle of partial size, and then influence
Dispersion in resin.In view of the above-mentioned problems, inventor herein uses for reference the experience of APP surface treatment and microcapsule coated, lead to
Cross to piperazine phosphate compound flame retardant carry out powder surface treatment and cladding, to improve the flame-retardant system mobility,
Dispersibility and water resistance.CN104672492A, which discloses organic silicone oil, can inhibit in the processing of piperazine phosphate compound flame retardant
Coke material.CN107075378A, which discloses silicone oil and silane coupling agent, to prevent fire retardant from agglomerating, and improve dispersibility, assign water-fast
Property and heat resistance.But fire retardant powder especially piperazine pyrophosphate is compounded by lubricant and the use of silicone oil material mixing
System carries out surface treatment and the research of microcapsule coated, improves reunion, agglomeration and the processing problems of piperazine pyrophosphate system, mentions
Its high water-fast, moisture absorption migration in anti-flaming polypropylene material is reported there has been no open.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind to improve simultaneously
The hydrophobicity of fire retardant and the resistance to precipitation halogen-free flame retardants of the high fluidity of mobility and its preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of high fluidity halogen-free flame retardants of resistance to precipitation, raw material include the component of following weight percentage:
Piperazine phosphate 45~70%；
Melamine and derivative 20~50%；
Inorganic metal zinc compound 5~10%；
Surface treating agent 0.1~1.5%；
Wherein, the surface treating agent includes lubricant and silicone oil substance, the matter of the lubricant and silicone oil substance
Amount is than being 0.5~1.2；
The silicone oil substance forms cyst wall outside the bulk powder of halogen-free flame retardants.
The present invention carries out at surface piperazine phosphate compound flame retardant by being used in mixed way lubricant and silicone oil substance
Reason and microcapsule coated, significantly improve the mobility, dispersibility and water resistance of compound flame retardant, to solve piperazine phosphate
Compounding flame retardant processes easy bridge formation problem, and then solve compounding flame retardant in resin there are powder reuniting, agglomeration
The problems such as dispersibility and poor compatibility.
Silicone oil has good chemical stability, insulating properties, and hydrophobic performance is good, but in experiments it is found that, only by silicon
Oily substance is added in the bulk powder of halogen-free flame retardants the water resistance and mobility that can not improve fire retardant, this is because
In the prior art, such as CN104672492A, silicone oil is only to be mixed into powder material, is modified to powder material, is prevented
Only burnt material phenomenon occurs for the piperazine phosphate of small molecule, and if it is intended to the water resistance and mobility of raising fire retardant, sufficiently benefit
With the hydrophobic group on silicone oil surface, needing, which coats silicone oil outside the bulk powder of halogen-free flame retardants, forms a microcapsules,
The hydrophobic effect of silicone oil can be given full play to.
For formula of the invention, the additive amount of surface treating agent is very crucial.If the addition of surface treating agent
Measure too low, then silicone oil cannot be completely dispersed fire-retardant powder body surface, prevent part powder surface from coating or cannot be complete
Full cladding silicon oil membrane, influences hydrophobic performance.If the adding too much of surface treating agent, formed in fire-retardant powder body surface
Coated Si oil film thickness increase, but hydrophobic performance does not have proportional enhancing, and powder diameter is caused to increase, and then influences anti-flammability
Can, while increasing processing cost；Only in the case where specific additive amount, cyst wall that silicone oil is formed on fire-retardant powder surface
Excellent hydrophobic performance is just shown, while not influencing the flame retardant property of fire retardant itself.
The viscosity of the silicone oil substance is 15~70mPas.
The silicone oil substance is selected from dimethicone, Methyl Hydrogen Polysiloxane Fluid, ethyl containing hydrogen silicone oil, aminomethyl phenyl silicon
One or more of oil, methylhydroxy silicone oil, Methylethyl silicone oil.
Why silicone oil can form cyst wall, be because silicone oil metal solvent effect under, can be crosslinked at moderate temperatures,
Hydrophobic membrane is formed in various substrate surfaces, cyst wall is formed in order to which silicone oil can be coated outside fire retardant powder, to fire retardant
Powder is protected, and the silicone oil substance of specific viscosity is needed.Certain relationship is presented in the viscosity and average molecular weight of silicone oil, such as
The viscosity of fruit silicone oil is too low, then average molecular weight is smaller, and Yi Qinshui influences hydrophobic performance；If the viscosity of silicone oil is excessively high, put down
Average molecular weight is larger, influences spraying and efficiency is added dropwise, be not easy to be uniformly dispersed in powder, may result in part powder cladding not
Completely.
The lubricant is selected from stearic amide, erucyl amide, butyl stearate, glycerol trihydroxy stearate, oleoyl
One or more of amine or ethylene bis stearamide.
Silicone oil, because having certain viscosity to be easy adhesion, influences powder after fire-retardant powder ontology forms hydrophobic membrane
Mobility.The dispersed lubricant in silicone oil passes through fire retardant powder after the lubrication of lubricant and buffer action raising processing
Mobility, while in resin extrusion molding, mobility can be improved, improve the adhesion of resin and barrel, prevent and reduce stagnant
Stay object.
The piperazine phosphate is selected from piperazine pyrophosphate, focuses one or both of piperazine phosphate mixture, wherein gathering
The molar ratio of phosphorus atoms and nitrogen-atoms is 1:1 in the repetitive unit of piperazine pyrophosphate molecular structure；The melamine and derivative
Object is selected from one of melamine, melamine cyanurate, Melamine octamolybdate or melamine borate salt or several
Kind；The inorganic metal zinc compound is selected from one or more of zinc oxide, anhydrous zinc borate, 3.5 hydrate zinc borates.
According to the close principle of polarity, a piperazine phosphate and diphosphonic acid piperazine are small molecule salt, the poor compatibility with resin, together
When small-molecule substance thermal stability it is poor, thermal decomposition temperature is low, due to shear heat in the extrusion process of acrylic resin
Thermal degradation is caused, burnt material is caused.And focusing piperazine phosphate is macromolecular backbone, and it is good with the compatibility of resin, at charcoal, heat
Stability is good, and excellent flame retardant property is shown in resin.
Wherein, the molecular structural formula of piperazine phosphate is focused are as follows:
The present invention also provides a kind of resistance to preparation methods that halogen-free flame retardants is precipitated of high fluidity, comprising the following steps:
The preparation of the bulk powder of halogen-free flame retardants:
Piperazine phosphate, melamine and derivative and inorganic metal zinc compound are put into high-speed mixer according to formula
In, then the moisture content in 250~600rpm of low speed mixing removal mixed material carries out high speed 800~1200rpm mixing and obtains institute
State the bulk powder of halogen-free flame retardants；
The preparation of surface treating agent:
Lubricant is distributed in silicone oil substance and obtains the surface treating agent；
The preparation of halogen-free flame retardants:
The powder sheet equipped with halogen-free flame retardants is added by way of spraying or dropwise addition in the surface treating agent being prepared
In the high-speed mixer of body, cooling discharging after mixed at high speed obtains the halogen-free flame retardants.
Wherein, in the preparation step of the bulk powder of the halogen-free flame retardants, by the aqueous of mixed material after mixed on low speed
Rate is down to 0~0.1%.
In the preparation step of the bulk powder of the halogen-free flame retardants, the time of mixed on low speed is 5~30min, the process
It is 80~120 DEG C that high speed, which mixes built-in temperature,.
In the preparation step of the halogen-free flame retardants, mixed at high speed built-in temperature is set as 80~150 DEG C, when mixed at high speed
Between for close 5~30min.
In halogen-free flame retardants preparation process, moisture removal is removed in low speed with high-speed mixer, and when high speed carries out the packet of silicone oil
Processing is covered, the control of revolving speed plays a significant role the broken of powder and uniformly mixing.Low speed is used in water removal, is being guaranteed
It, can be to avoid the fugitive dust and loss of material of powder under the premise of powder reuniting particle is broken；The cladding stage using high speed, guarantees
Silicone oil being uniformly dispersed in powder makes powder surface form cyst wall similar in thickness.The revolving speed of high-speed mixer is bigger, kinetic energy
Bigger, the range of speeds in the present invention is high-speed mixer rotary speed parameter general in market, and equipment is easy to get, convenient to carry out.
In preparation process of the invention, the water content in the bulk powder of halogen-free flame retardants is very crucial, needs to exist in advance
Mixed on low speed removes the moisture content in material at a temperature of 80~120 DEG C or so, because fire-retardant powder ontology moisture content is compared with Gao Rong
Easy to reunite, high temperature water removal can make the little particle reunited easily be broken in mixed on low speed, and powder is uniformly dispersed, and carry out surface
When processing, surface forms uniform hydrophobic membrane, reduces agglomerated particle, improves hydrophobicity.If not removing the moisture content in material,
The little particle that fire retardant powder has been reunited when mixed on low speed is not easy to be broken, and short grained powder is coated togather by silicone oil, shadow
The dispersion of powder, is easy to form white point in resin, influences product and apparently spend when ringing processing.
Pre-treatment step of the invention, the hydrophobicity and product for not only increasing halogen-free flame retardants are apparently spent, also significantly
Reduce the type selecting difficulty to high-speed mixing equipment, in Chinese patent CN104672492A, in order to obtain preferable product table
Sight degree, the FM mixing machine used need to stir 10 minutes under the conditions of 120 DEG C with the revolving speed of 2800rpm, the high revolving speed of 2800rpm
Very unfavorable to lectotype selection, the present invention substantially reduces mixing revolving speed, using 800 by simple dehydration pre-process step
The revolving speed of~1200rpm can reach mixed effect, can be realized using common machine.
In addition, surface treating agent needs to pass through specific mode --- powder spraying and that addition halogen-free flame retardants is slowly added dropwise
In last ontology, and mixed at high speed should be needed in the process, and allow surface treating agent to be evenly coated at powder surface, crosslink, shape
At cyst wall.
The present invention also provides a kind of resistance to applications that halogen-free flame retardants is precipitated of high fluidity, and the halogen-free flame retardants is added poly-
The mobility and water resistance of acrylic resin are improved in allyl resin；The additional amount of the halogen-free flame retardants is the flame-retardant polypropylene
The 22~28% of olefine resin gross mass.
Halogen-free flame retardants in the present invention can be used in acrylic resin, and acrylic resin is homopolypropylene, copolymerization
The mixture of polypropylene and homopolymerization and copolymer polypropylene.In Intumscent Flame Retardant System, piperazine phosphate plays carbon source, acid source
Effect, melamine and derivative play a part of gas source, and acrylic resin itself also has part carbon source, and three sources need appropriate ratio
Example can just play good synergistic fire retardation.And the melt strength of resin matrix also will affect the charcoal that is expanded into of fire retardant, because
This compound flame retardant additive amount in the acrylic resin of the different trades mark is different, and component proportion slightly difference, what is shown is fire-retardant
Performance also slightly has difference.By the study found that performance of this flame retardant formulations in copolymer polypropylene can more preferably pass through
Extruding pelletization and injection molding.
Compared with prior art, the invention has the following advantages that
(1) modified to piperazine phosphate compound flame retardant by lubricant and silicone oil substance, improve its mobility, dispersion
Property and water resistance, the anti-flaming polypropylene material that fire retardant of the invention is added by experimental test can be small by 70 DEG C × 168
When submerging test (UL746C) and double 85 steady damp heat test (GB/T2423.50-2012,168h), further widen Halogen
Anti-flaming polypropylene material is in household electrical appliances, the application of automobile and other industries；
(2) additive amount of fire retardant of the invention in acrylic resin can achieve vertical combustion at 22~28%
Grade V-0 (1.6mm) grade, shows its excellent fireproof performance；
(3) preparation process is simple, by specifically removing water treatment steps, cooperates preferred silicone oil, successfully coats silicone oil
In fire retardant body exterior, cyst wall is formed, the hydrophobic effect of silicone oil is given full play to.
Detailed description of the invention
Fig. 1 is the contact angle photo of the halogen-free flame retardants in the present invention；
Fig. 2 is the contact angle photo of the fire retardant powder in comparative example 2.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
A kind of high fluidity halogen-free flame retardants of resistance to precipitation, raw material include the component of following weight percentage: piperazine phosphorus
Hydrochlorate 45~70%；Melamine and derivative 20~50%；Inorganic metal zinc compound 5~10%；Surface treating agent 0.1~
1.5%；Wherein, the surface treating agent includes lubricant and silicone oil substance, the quality of the lubricant and silicone oil substance
Than being 0.5~1.2；The silicone oil substance forms cyst wall outside the bulk powder of halogen-free flame retardants.
The following are the specific choices of each component:
Piperazine phosphate is selected from piperazine pyrophosphate, focuses one or both of piperazine phosphate mixture, wherein focusing phosphorus
The molar ratio of phosphorus atoms and nitrogen-atoms is 1:1 in the repetitive unit of mcpp acid molecular structure；Melamine and derivative are selected from three
One kind or two kinds of poly cyanamid (MA), melamine cyanurate (MCA), Melamine octamolybdate, melamine borate salt
Above mixture.Melamine and derivative mainly play action of gas source in compounding expansion type flame retardant, wherein it is preferred that three
Poly cyanamid (MA) or melamine cyanurate (MCA).
Inorganic metal zinc compound is selected from zinc oxide (ZnO), anhydrous zinc borate (2ZnO3B2O3), 3.5 hydrate zinc borates
(2ZnO·3B2O3·3.5H2One kind or two kinds of) O the mixture more than.
In surface treating agent, the viscosity range of silicone oil substance are as follows: 15~70mPas, silicone oil substance include dimethyl
One of silicone oil, Methyl Hydrogen Polysiloxane Fluid, ethyl containing hydrogen silicone oil, methyl phenyl silicone oil, methylhydroxy silicone oil, Methylethyl silicone oil
Or mixture of more than two kinds.Lubricant is selected from stearic amide, erucyl amide, butyl stearate, glycerol trihydroxy stearic acid
Mixture more than one kind or two kinds of ester, oleamide or ethylene bis stearamide.
The resistance to preparation process that halogen-free flame retardants is precipitated of above-mentioned high fluidity are as follows:
(1) preparation of the bulk powder of halogen-free flame retardants:
Piperazine phosphate, melamine and derivative and inorganic metal zinc compound are existed according to formula investment preheating temperature
In 80~120 DEG C of 300L high-speed mixer, 250~600rpm of low speed mixes 5~30min, removes the moisture content in material, then
Go to the bulk powder that high speed 800~1200rpm mixing obtains the halogen-free flame retardants；
(2) preparation of surface treating agent:
Lubricant is distributed in silicone oil substance and obtains the surface treating agent；
(3) preparation of halogen-free flame retardants:
The powder sheet equipped with halogen-free flame retardants is added by way of spraying or dropwise addition in the surface treating agent being prepared
In the high-speed mixer of body, temperature is at 80~150 DEG C, and high-speed stirred mixes 5~30min, and then cooling discharging, obtains the nothing
Halogen fire retardant.Since silicone oil substance has certain viscosity, the dispersion of silicone oil can be improved by spraying mode, if dress
It sets and does not prepare by spraying, can also be realized by way of being slowly added dropwise.According further to compound preparation time temperature equivalence principle,
Specific processing temperature and time adjust according to the actual situation.
The resistance to precipitation halogen-free flame retardants of the high fluidity that the above method is prepared is added in acrylic resin, obtains fire-retardant
Material；The additional amount of the halogen-free flame retardants is the 22~28% of the flame retardant polypropylene resin gross mass.
The extruding pelletization process of fire proofing are as follows: it is stirred in height and acrylic resin is added in machine, a small amount of white oil premix is added,
Then treated compound flame retardant is added, is wrapped in powder uniformly on resin particle.By each area's temperature of double screw extruder
Polypropylene particles are added after stablizing 20min in predetermined temperature in degree setting from hopper, by tie rod, pelletizing, drying, complete to squeeze
It is granulated out.
Fire proofing will be obtained to carry out using test: the fire-retardant particle after drying is molded into various tests in injection molding machine
The standard sample of prescribed by standard, and carry out the test of associated materials performance.
Following performance indicator is mainly tested to the fire retardant of surface treatment front and back:
A, mobility
Powder passes through the gross mass that metal funnel falls naturally at the appointed time for measurement.
B, contact angle
It is using double-sided adhesive, powder is evenly laid out on glass slide, with contact angle instrument measurement deionized water in powder
On contact angle, contact angle is higher, and the hydrophobicity of powder is stronger.
C, partial size
It is carried out by GB/T 19077, measures powder X50Particle size, judge powder coat situation.
Anti-flaming polypropylene material is primarily upon following performance indicator:
A, flame retardant property
It is carried out by GB/T 2408-2008, when sample thickness is 1.6mm, UL746C and double 85 tests the vertical of front and back sample
Combustibility.
B, resistance to migration experiment
It in temperature is respectively 70 DEG C by the standard sample prepared according to UL746C and GB/T 2423.50-2012 standard
Water in impregnate 168h, 168h, visual observations specimen surface are placed in 85 DEG C of temperature, the climatic chamber of relative humidity 85%
Powder state.
The following are specific implementation process of the invention.
Embodiment 1
A kind of high fluidity halogen-free flame retardants of resistance to precipitation, composition of raw materials is as shown in table 1, and preparation process is by piperazine phosphoric acid
Salt, melamine and derivative, metal zinc compound each component proportionally launch the 300L high speed to preheating temperature at 120 DEG C
In mixing machine, low speed 475rpm mixing 10min removes the moisture content (water content is reduced to 0.1% or less) in material, then goes to
The silicone oil substance for being dispersed with lubricant is uniformly sprayed onto kettle, mixed at high speed by high speed 1000rpm mixing by spraying device
Then 15min is cooled down, discharging obtains the uniformly mixed compounding flame retardant being surface-treated, gained powder and testing of materials
It the results are shown in Table 1；The silicone oil viscosity that the present embodiment uses is 50mPas.
Embodiment 2
Implementation process is same as Example 1, except the preheating temperature of 300L kettle in the surface treatment process of compound flame retardant is
150 DEG C, the mixed at high speed time is 5min.Unclassified stores and proportion are shown in Table 1, and gained powder and testing of materials the results are shown in Table 1, this reality
Silicone oil viscosity that example uses is applied as 60mPas.
The hydrophobicity for the surface treatment fire retardant that the embodiment obtains is tested, the contact angle of halogen-free flame retardants is obtained
Photo, as shown in Figure 1, discovery distilled water is distributed in the fire retardant powder surface in droplet shape, contact angle is 160 °, shows the powder
The hydrophobicity of body is preferable.
Embodiment 3
Implementation process is same as Example 1, except the preheating temperature of 300L kettle in the surface treatment process of compound flame retardant is
100 DEG C, the mixed at high speed time is 20min.Unclassified stores and proportion are shown in Table 1, and gained powder and testing of materials the results are shown in Table 1, this
The silicone oil viscosity that embodiment uses is 15mPas.
Embodiment 4
Implementation process is same as Example 1, except the preheating temperature of 300L kettle in the surface treatment process of compound flame retardant is
80 DEG C, the mixed at high speed time is 30min.Unclassified stores and proportion are shown in Table 1, and gained powder and testing of materials the results are shown in Table 1, this reality
Silicone oil viscosity that example uses is applied as 70mPas.
Embodiment 5~8
Implementation process is same as Example 1, and unclassified stores and proportion are shown in Table 1, and gained powder and testing of materials the results are shown in Table
1。
Comparative example 1~4
1~4 implementation process of comparative example corresponds respectively to the embodiment of Examples 1 to 4, and difference is to be not added in component
Enter the surface treating agent of lubricant and silicone oil substance, unclassified stores and proportion are shown in Table 2, and gained powder and testing of materials result are shown in
Table 2.
The hydrophobicity of fire retardant powder in comparative example 2 is tested, the contact angle photo of halogen-free flame retardants is obtained,
As shown in Fig. 2, discovery distilled water infiltrates spread apart in the fire retardant powder surface, contact angle is 0 °, and the hydrophobicity of powder is poor,
Do not have hydrophobic effect.
Comparative example 5
The implementation process of comparative example 5 is substantially the same manner as Example 1, and difference is the piperazine phosphorus obtained during the preparation process
Hydrochlorate, melamine and derivative, metallic zinc compound powder stir at low speed dehydration without heating, measure and are prepared
Mixture of powders water content be 0.38%, it is higher, unclassified stores and proportion be shown in Table 2, gained powder and testing of materials result are shown in
Table 2.
Comparative example 6
The implementation process of comparative example 6 is substantially the same manner as Example 1, and difference is that the silicone oil viscosity of selection is larger, is
100mPas, unclassified stores and proportion are shown in Table 2, and gained powder and testing of materials the results are shown in Table 2.
Comparative example 7
Comparative example 7 is the fire retardant being prepared using the embodiment 8 in Chinese patent CN 104672492A, tests it
Water resistance and mobility, gained powder and testing of materials the results are shown in Table 2.
Flame retardant formulations (in parts by weight) and test result in 1 embodiment of table
Flame retardant formulations (in parts by weight) and test result in 2 comparative example of table
By comparing the data of comparative example 1~4 in Tables 1 and 2, we are not it can be found that if add silicone oil and lubrication
The mobility of agent, fire retardant powder is reduced to 5.32~8.01g/3min from 14.63~19.82g/3min, greatly reduces resistance
The mobility of agent is fired, and 153 ° minimum to the contact angle of water of material in embodiment, or directly presents and can not contact powder
The phenomenon that body, shows it with good hydrophobic effect, and the hydrophobic angle in comparative example is 0 °, shows silicone oil and lubricant is
Improve the key component of material hydrophobic and mobility.In addition, further testing flame retardant property, the fire retardant in embodiment is found
Superior flame retardant property, flame retardant rating is V-0, and resistance to migration is preferable, and the fire proofing surface of acquisition is substantially without powder.
In addition, comparing embodiment 1 and comparative example 5, it is found that if not carrying out dehydration pre-process to fire retardant powder,
Fire retardant is added and starts to spray surface treating agent in 300L kettle, silicone oil Quick cross-linking film-forming at 120 DEG C is coated on
Fire-retardant powder body surface, including the not pulverized short grained surface of piperazine pyrophosphate of having reunited, contact angle reaches
139 °, there is certain hydrophobicity, but the mobility of fire retardant reduces, diameter of particle X50Increase, influences fire retardant powder and exist
Dispersibility in resin, PP resin spline surfaces have slight white point；
Comparing embodiment 1 and comparative example 6, it is found that if the viscosity of silicone oil is excessive, surface treating agent spray time compared with
Long, processing efficiency reduces, while viscosity increases, and the specific gravity of silicone oil is bigger, and silicone oil is easy to collide high speed agitator, quilt when spraying
It is thrown to kettle wall, practical silicone oil covering amount is reduced, and is dispersed unevenly, and powder cladding not exclusively, shows that contact angle is reduced to
112 °, the flame retardant property after double 85 tests is reduced to V-1 grades, and spline surfaces powder increases, and resistance to migration reduces.
Due to not carrying out hydrophobicity and fluidity testing to the material of acquisition in 104672492 A of Chinese patent CN, it is
In contrast, fire retardant combination has been prepared according to the formula and preparation method of embodiment 8 in the present invention, using with it is poly-
In allyl resin, discovery fire retardant does not pass through dehydration pre-process, and in 120 DEG C of stirring 10min, the processing time is slightly shorter, cannot
Complete coated by hydrophobic film is formed, contact angle is only 103 °, and hydrophobicity and mobility reduce, batten after UL746C and double 85 is tested
Anti-flammability decline, powder moisture absorption moves to surface, shows silicone oil and monoesters chemical combination in 104672492 A of Chinese patent CN
Object cooperates the hydrophobicity and mobility that can not significantly improve material.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (9)
1. a kind of high fluidity halogen-free flame retardants of resistance to precipitation, which is characterized in that its raw material includes the group of following weight percentage
Point:
Wherein, the surface treating agent includes lubricant and silicone oil substance, the mass ratio of the lubricant and silicone oil substance
It is 0.5~1.2；The viscosity of the silicone oil substance is 15~70mPas；
The silicone oil substance forms cyst wall outside the bulk powder of halogen-free flame retardants.
2. a kind of high fluidity halogen-free flame retardants of resistance to precipitation according to claim 1, which is characterized in that the silicone oil object
Matter is selected from dimethicone, Methyl Hydrogen Polysiloxane Fluid, ethyl containing hydrogen silicone oil, methyl phenyl silicone oil, methylhydroxy silicone oil, Methylethyl
One or more of silicone oil.
3. a kind of high fluidity halogen-free flame retardants of resistance to precipitation according to claim 1, which is characterized in that the lubricant choosing
From in stearic amide, erucyl amide, butyl stearate, glycerol trihydroxy stearate, oleamide or ethylene bis stearamide
One or more.
4. a kind of high fluidity halogen-free flame retardants of resistance to precipitation according to claim 1, which is characterized in that the piperazine phosphoric acid
Salt is selected from piperazine pyrophosphate or focuses one or both of piperazine phosphate mixture.
5. a kind of high fluidity halogen-free flame retardants of resistance to precipitation according to claim 1, which is characterized in that the melamine
And derivative in melamine, melamine cyanurate, Melamine octamolybdate or melamine borate salt one
Kind is several；The inorganic metal zinc compound is selected from one or more of zinc oxide, anhydrous zinc borate, 3.5 hydrate zinc borates.
6. a kind of resistance to preparation method that halogen-free flame retardants is precipitated of high fluidity as described in claim 1, which is characterized in that including
Following steps:
The preparation of the bulk powder of halogen-free flame retardants:
Piperazine phosphate, melamine and derivative and inorganic metal zinc compound are put into high-speed mixer according to formula,
Moisture content under the conditions of 250~600rpm in mixed on low speed removal mixed material, then under the conditions of 800~1200rpm at a high speed
Mixing obtains the bulk powder of the halogen-free flame retardants；
The preparation of surface treating agent:
Lubricant is distributed in silicone oil substance and obtains the surface treating agent；
The preparation of halogen-free flame retardants:
The bulk powder equipped with halogen-free flame retardants is added by way of spraying or dropwise addition in the surface treating agent being prepared
In high-speed mixer, cooling discharging after mixed at high speed obtains the halogen-free flame retardants.
7. a kind of resistance to preparation method that halogen-free flame retardants is precipitated of high fluidity according to claim 6, which is characterized in that institute
In the preparation step for stating the bulk powder of halogen-free flame retardants, the moisture content of mixed material is down to 0~0.1% after mixed on low speed.
8. a kind of resistance to preparation method that halogen-free flame retardants is precipitated of high fluidity according to claim 6, which is characterized in that institute
In the preparation step for stating the bulk powder of halogen-free flame retardants, the time of mixed on low speed is 5~30min, mixed at high speed during being somebody's turn to do
Built-in temperature is 80~120 DEG C；In the preparation step of the halogen-free flame retardants, mixed at high speed built-in temperature is set as 80~150
DEG C, the mixed at high speed time is to close 5~30min.
9. a kind of resistance to application that halogen-free flame retardants is precipitated of high fluidity as described in claim 1, which is characterized in that the Halogen
The mobility and water resistance for improving acrylic resin is added in acrylic resin in fire retardant；The additional amount of the halogen-free flame retardants is
The 22~28% of the flame retardant polypropylene resin gross mass.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112409693A (en) * | 2020-11-26 | 2021-02-26 | 浙江旭森非卤消烟阻燃剂有限公司 | Halogen-free flame retardant with good flame retardance and processability and flame-retardant resin composition |
| CN112876739A (en) * | 2021-01-22 | 2021-06-01 | 深圳市锦昊辉实业发展有限公司 | Preparation method of halogen-free flame retardant, halogen-free flame retardant and sealant |
| CN113388193A (en) * | 2021-05-06 | 2021-09-14 | 上海化工研究院有限公司 | Anti-yellowing halogen-free flame-retardant polyolefin composition and preparation method thereof |
| CN114395291A (en) * | 2022-01-21 | 2022-04-26 | 东莞市宏泰基阻燃材料有限公司 | Efficient halogen-free flame retardant for printing ink and preparation method and application thereof |
| CN115772285A (en) * | 2022-12-12 | 2023-03-10 | 云南云天化股份有限公司 | Preparation method of modified piperazine pyrophosphate and modified piperazine pyrophosphate |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19830128A1 (en) * | 1998-07-06 | 2000-02-10 | Degussa | Surface modified flame retardants, processes for their production and their use |
| JP2004051990A (en) * | 2002-07-16 | 2004-02-19 | Shin Etsu Chem Co Ltd | Organo-polysiloxane-coated powder and its production method |
| CN1664019A (en) * | 2005-03-02 | 2005-09-07 | 江苏宏达化工新材料股份有限公司 | Dynamic high temperature treatment method for aluminium hydroxide for silicon rubber flame-retardant additives |
| CN1847362A (en) * | 2006-05-11 | 2006-10-18 | 华东理工大学 | Expansion type fireproof moisture-resisting phosphorus-nitrogen material and its prepn |
| CN1922260A (en) * | 2004-02-24 | 2007-02-28 | 株式会社艾迪科 | Flame retardant composition with enhanced fluidity, flame retardant resin composition and molding thereof |
| CN102031025A (en) * | 2010-10-20 | 2011-04-27 | 中科院广州化学有限公司 | Method for preparing silicone oil surface modified aluminium hydroxide flame retardant |
| US20130338280A1 (en) * | 2012-06-19 | 2013-12-19 | International Business Machines Corporation | Flame Retardant Material with Orthogonally Functional Capsules |
| CN104479172A (en) * | 2014-12-05 | 2015-04-01 | 黑龙江省润特科技有限公司 | Preparation method of ammonium polyphosphate wrapped with fluorine-containing silicone oil on surface |
| CN104672492A (en) * | 2007-11-14 | 2015-06-03 | 株式会社艾迪科 | Flame Retardant Composition Having Improved Processability, Flame-retardant Synthetic Resin Composition, And Molded Article Of The Flame-retardant Synthetic Resin Composition |
| CN105504519A (en) * | 2016-01-25 | 2016-04-20 | 上海捷棉新材料科技有限公司 | Halogen-free environment-friendly flame-retardant polyolefin master batch for replacing bromine-containing flame retardant and preparation method of master batch |
-
2019
- 2019-09-29 CN CN201910933789.9A patent/CN110483898B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19830128A1 (en) * | 1998-07-06 | 2000-02-10 | Degussa | Surface modified flame retardants, processes for their production and their use |
| JP2004051990A (en) * | 2002-07-16 | 2004-02-19 | Shin Etsu Chem Co Ltd | Organo-polysiloxane-coated powder and its production method |
| CN1922260A (en) * | 2004-02-24 | 2007-02-28 | 株式会社艾迪科 | Flame retardant composition with enhanced fluidity, flame retardant resin composition and molding thereof |
| CN1664019A (en) * | 2005-03-02 | 2005-09-07 | 江苏宏达化工新材料股份有限公司 | Dynamic high temperature treatment method for aluminium hydroxide for silicon rubber flame-retardant additives |
| CN1847362A (en) * | 2006-05-11 | 2006-10-18 | 华东理工大学 | Expansion type fireproof moisture-resisting phosphorus-nitrogen material and its prepn |
| CN104672492A (en) * | 2007-11-14 | 2015-06-03 | 株式会社艾迪科 | Flame Retardant Composition Having Improved Processability, Flame-retardant Synthetic Resin Composition, And Molded Article Of The Flame-retardant Synthetic Resin Composition |
| CN102031025A (en) * | 2010-10-20 | 2011-04-27 | 中科院广州化学有限公司 | Method for preparing silicone oil surface modified aluminium hydroxide flame retardant |
| US20130338280A1 (en) * | 2012-06-19 | 2013-12-19 | International Business Machines Corporation | Flame Retardant Material with Orthogonally Functional Capsules |
| CN104479172A (en) * | 2014-12-05 | 2015-04-01 | 黑龙江省润特科技有限公司 | Preparation method of ammonium polyphosphate wrapped with fluorine-containing silicone oil on surface |
| CN105504519A (en) * | 2016-01-25 | 2016-04-20 | 上海捷棉新材料科技有限公司 | Halogen-free environment-friendly flame-retardant polyolefin master batch for replacing bromine-containing flame retardant and preparation method of master batch |
Non-Patent Citations (2)
| Title |
|---|
| BIBOWANG，ET AL.: "Recent advances for microencapsulation of flame retardant", 《POLYMER DEGRADATION AND STABILITY》 * |
| 钱汉英等编: "《塑料加工实用技术问答》", 31 July 2001, 机械工业出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112409693A (en) * | 2020-11-26 | 2021-02-26 | 浙江旭森非卤消烟阻燃剂有限公司 | Halogen-free flame retardant with good flame retardance and processability and flame-retardant resin composition |
| CN112409693B (en) * | 2020-11-26 | 2023-05-09 | 浙江旭森阻燃剂股份有限公司 | Halogen-free flame retardant with good flame retardance and processability and flame-retardant resin composition |
| CN112876739A (en) * | 2021-01-22 | 2021-06-01 | 深圳市锦昊辉实业发展有限公司 | Preparation method of halogen-free flame retardant, halogen-free flame retardant and sealant |
| CN112876739B (en) * | 2021-01-22 | 2022-11-04 | 深圳市锦昊辉实业发展有限公司 | Preparation method of halogen-free flame retardant, halogen-free flame retardant and sealant |
| CN113388193A (en) * | 2021-05-06 | 2021-09-14 | 上海化工研究院有限公司 | Anti-yellowing halogen-free flame-retardant polyolefin composition and preparation method thereof |
| CN114395291A (en) * | 2022-01-21 | 2022-04-26 | 东莞市宏泰基阻燃材料有限公司 | Efficient halogen-free flame retardant for printing ink and preparation method and application thereof |
| CN115772285A (en) * | 2022-12-12 | 2023-03-10 | 云南云天化股份有限公司 | Preparation method of modified piperazine pyrophosphate and modified piperazine pyrophosphate |
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