CN104017220A - A high-molecular-weight crosslinking polyphosphoester halogen-free fire retardant and a preparing method thereof - Google Patents
A high-molecular-weight crosslinking polyphosphoester halogen-free fire retardant and a preparing method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of novel materials, and particularly relates to a high-molecular-weight crosslinking polyphosphoester halogen-free fire retardant and a preparing method thereof. The structural formula of the halogen-free fire retardant is described in the specification, wherein R is selected from arylidene or alkylene. The fire retardant comprises following raw materials by mole: 1.0 part of ammonium polyphosphate, 0.2-0.8 part of a hydroxy compound and 0.01-0.06 part of a catalyst. The crosslinking high-molecular-weight polymer is obtained by adoption of organic high-molecular-weight polymer synthetic methods, such as polycondensation and crosslinking reactions, and the water tolerance and heat resistance of the product are largely improved. The high-molecular-weight crosslinking polyphosphoester halogen-free fire retardant is prepared by the preparing method. The fire retardant integrates advantages of the ammonium polyphosphate and phosphoester and overcomes disadvantages of the phosphoester and the ammonium polyphosphate at the same time.
Description
Technical field
The invention belongs to new material technology field, be specially crosslinked calcium polyphosphate ester halogen-free flame retardants of a kind of high molecular and preparation method thereof.
Background technology
Although the flame retardant effect of tradition bromide fire retardant is fine, because wherein a considerable part is unfriendly to environment, even humans and animals is produced to very large harm, for example Poly Brominated Diphenyl Ethers series.The fire retardant mechanism of halogen flame is gas phase fire retardant mechanism, be after inflammable gas discharges, the hydrogen halide that fire retardant discharges, at gas phase Mulberry Extract, can not continue burning, therefore, no matter whether burn, in the time being heated, all discharge a large amount of obnoxious flavoures, human and environment is worked the mischief, the hydrogen halide particularly discharging has very strong pungency, airborne concentration is slightly large, just can allow people suffocate, and hydrogen halide also has deep-etching effect simultaneously.
In view of halogen flame has huge hazardness to human and environment, halogen-free flame retardants has just become people's the direction of chasing, and phosphorus flame retardant is the most important thing in halogen-free flame retardants.Although phosphorus is flame retardant effect, because it is more friendly to environment, there is no any harm, therefore, its use range is more and more wide, and people also more and more pay attention to it, and demand increases year by year.
Phosphonium flame retardant mainly works in condensed phase, and its fire retardant mechanism is as follows:
Phosphonium flame retardant is at high temperature decomposed to form phosphoric acid or metaphosphoric acid as strong dewatering agent, promotes that matrix resin becomes charcoal, and discharges water vapor, and the generation of charcoal has reduced the thermal conduction from flame to condensed phase; Form the glass or liquid protective layer of thin layer on condensed phase surface; therefore reduce heat and mass transfer between oxygen diffusion and gas phase and solid phase, suppressed char combustion process, reduced the generation of heat; suppress the rising of temperature, thereby reached fire-retardant object.Produce because solid phase fire retardant mechanism does not almost have obnoxious flavour, meanwhile, the toxicity of phosphorus flame retardant itself is very little, so, be the friendly fire retardant series to human and environment.
Phosphorus flame retardant is mainly divided into inorganic phosphorus system and organic phosphorus flame retardant.The topmost product of inorganic phosphor-contained fire retardant has red phosphorus combustion inhibitor, ammonium phosphate salt and ammonium polyphosphate etc.Wherein ammonium polyphosphate is subject to people's attention, and is widely used in frie retardant coating industry, but also has a lot of defects to overcome at polymeric material field as fire retardant.Be that the solubleness of ammonium polyphosphate in water is too large on the one hand, and the consistency of resin base material is poor, easily from material, separates out; On the other hand, ammonium polyphosphate decomposition temperature is low, more than 200 DEG C, can decomposite ammonia, particularly under stronger shear action, more obvious.
It is that phosphoric acid ester, butylbenzene are phosphoric acid ester etc. that organic phosphorus flame retardant has mainly contained triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene.The feature of phosphoric acid ester is to have fire-retardant and plasticising dual-use function.It is non-halogen that it can make fire retardant realize, and when its plasticising function can make plastic shaping, flow processability improves, and can suppress the resistates after burning.The poisonous gas and the corrosive gases that produce are fewer than halogenated flame retardant.Its major advantage is that efficiency is higher; Impact on photostabilizer effect is less; In processing and burning, corrodibility is little; There is the effect that hinders resume combustion; Seldom or not increase the quality of fire retardant material.But most of phosphoric acid ester fire retardants also exist some shortcomings.As poor heat resistance, volatility is large, consistency is undesirable etc., has greatly reduced the heat-drawn wire of material simultaneously, when have heat-resisting and rigidity to require to material, just can not do fire retardant by phosphoric acid ester.
Summary of the invention
The object of the invention is the poor water resistance for ammonium polyphosphate in prior art, easily decompose the defect of easily separating out; Phosphoric acid ester fire retardant poor heat resistance, volatility is large, consistency is undesirable, has greatly reduced the problem such as heat-drawn wire of material simultaneously, and a kind of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular is provided.
Another one goal of the invention of the present invention is to provide a kind of preparation method of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular.
To achieve these goals, concrete technical scheme of the present invention is:
A crosslinked calcium polyphosphate ester halogen-free flame retardants for high molecular, the structural formula of this halogen-free flame retardants is
R is wherein selected from arylidene or alkylidene group.Described R group is selected from the one in following substituting group:
The crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, comprises following raw material: ammonium polyphosphate, dihydroxy compound and catalyzer; Wherein, the molfraction of each feed composition is as follows:
1.0 parts of ammonium polyphosphates
Dihydroxy compound 0.2-0.8 part
Catalyzer 0.001-0.06 part.
As preferably, in the crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, the molfraction of each component is:
1.0 parts of ammonium polyphosphates
Dihydroxy compound 0.4-0.6 part
Catalyzer 0.01-0.02 part
Wherein, the mole number of ammonium polyphosphate is by phosphoric acid mole number.
The crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, reacts by following reaction formula:
Wherein m+n=2p.
Described dihydroxy compound raw material comprises ethylene glycol, propylene glycol, hexylene glycol, dihydroxyphenyl propane, the mixture of one or more in Resorcinol; Described catalyzer is antimony glycol, Lithium Acetate, aluminum oxide, calcium oxide, cobalt oxalate, silicon oxide, the mixture of one or more in titanium oxide; Described ammonium polyphosphate is II type long-chain ammonium polyphosphate, and the polymerization degree is greater than 1000.
The preparation method of the crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, comprises the following steps:
(1), according to said ratio, ammonium polyphosphate, dihydroxy compound, catalyzer are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 200-260 DEG C; The temperature of forcing machine is preferably 240-250 DEG C.
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 280-350 DEG C; Temperature in Banbury mixer or High Temperature Furnaces Heating Apparatus is controlled at 310-320 DEG C.
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
Positively effect of the present invention is:
(1) the present invention adopts organic high molecular polymer synthetic method, and as polycondensation, crosslinking reaction etc., have obtained cross-linked polymer polymkeric substance, and the water tolerance of product and thermotolerance are greatly improved.
(2), make a kind of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular by the present invention, combine the advantage of ammonium polyphosphate and phosphoric acid ester, overcome both shortcomings simultaneously.
embodiment
The crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, comprises following raw material: ammonium polyphosphate, dihydroxy compound and catalyzer; Wherein, the molfraction of each feed composition is as follows:
1.0 parts of ammonium polyphosphates
Dihydroxy compound 0.2-0.8 part
Catalyzer 0.001-0.06 part.
As preferably, in the crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, the molfraction of each component is:
1.0 parts of ammonium polyphosphates
Dihydroxy compound 0.4-0.6 part
Catalyzer 0.01-0.02 part
Wherein, the mole number of ammonium polyphosphate is by phosphoric acid mole number.Dihydroxy compound raw material comprises ethylene glycol, propylene glycol, hexylene glycol, dihydroxyphenyl propane, the mixture of one or more in Resorcinol; Described catalyzer is antimony glycol, Lithium Acetate, aluminum oxide, calcium oxide, cobalt oxalate, silicon oxide, the mixture of one or more in titanium oxide; Described ammonium polyphosphate is II type long-chain ammonium polyphosphate, and the polymerization degree is greater than 1000.
The crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, reacts by following reaction formula:
Wherein m+n=2p.
The preparation method of the crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, comprises the following steps:
(1), according to said ratio, ammonium polyphosphate, dihydroxy compound, catalyzer are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 200-260 DEG C; The temperature of forcing machine is preferably 240-250 DEG C.
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 280-350 DEG C; Temperature in Banbury mixer or High Temperature Furnaces Heating Apparatus is controlled at 310-320 DEG C.
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
The crosslinked calcium polyphosphate ester halogen-free flame retardants of the high molecular of preparing according to above raw material and method, structural formula be:
R is wherein selected from arylidene or alkylidene group.Described R group is selected from the one in following substituting group:
The present invention adopts crosslinked polymeric synthesis technique, forms the thermoset phosphorous polymer of high molecular or ultra-high molecular weight, just efficiently solves water resistance of ammonium polyphosphate poor, easily decomposes the problem of easily separating out; Also solved phosphoric acid ester fire retardant poor heat resistance, volatility is large, consistency is undesirable, has greatly reduced the problem such as heat-drawn wire of material simultaneously.
Below in conjunction with specific examples, the present invention is explained in detail to explanation.
But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacements and change, all should comprise within the scope of the invention.
According to general plotting of the present invention, contriver has manufactured experimently the crosslinked calcium polyphosphate ester halogen-free flame retardants of the high molecular of many batches of different ingredients components and processing condition, and measures by the following method the correlated performance parameter of comparative example and each embodiment sample:
(1), thermotolerance:
In 280 DEG C of warm airs, heat 1 hour, measure the weight loss on heating of 280 DEG C.
Quality product before M0 heating
Quality product after M1 heating
P weight loss on heating
P＝(1—M1/M0)╳100％
(2), the solubleness in water according to GB/T21845-2008 test fire retardant.
(3), according to the phosphorus content of GB/T23942-2009 test fire retardant.
Comparative example 1
Commercially available II type long-chain ammonium polyphosphate, the polymerization degree is greater than 1000.
Comparative example 2
Commercially available triphenylphosphate.
Embodiment 1:
A kind of preparation method of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, described raw material comprises ammonium polyphosphate, dihydroxy compound, catalyzer, wherein, the molfraction of the each component of raw material (mole number of ammonium polyphosphate is by phosphoric acid mole number) ratio is as follows:
1.0 parts of ammonium polyphosphates
0.2 part of dihydroxyphenyl propane
0.001 part of antimony glycol
As preferably, preparation method comprises the steps:
(1), according to said ratio, ammonium polyphosphate, dihydroxyphenyl propane, antimony glycol are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 200 DEG C;
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 280 DEG C;
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
Embodiment 2:
A kind of preparation method of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, described raw material comprises ammonium polyphosphate, dihydroxy compound, catalyzer, wherein, the molfraction of the each component of raw material (mole number of ammonium polyphosphate is by phosphoric acid mole number) ratio is as follows:
1.0 parts of ammonium polyphosphates
0.8 part of ethylene glycol
0.06 part of cobalt oxalate
As preferably, preparation method comprises the steps:
(1), according to said ratio, ammonium polyphosphate, ethylene glycol, cobalt oxalate are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 260 DEG C;
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 350 DEG C;
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
Embodiment 3:
A kind of preparation method of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, described raw material comprises ammonium polyphosphate, dihydroxy compound, catalyzer, wherein, the molfraction of the each component of raw material (mole number of ammonium polyphosphate is by phosphoric acid mole number) ratio is as follows:
1.0 parts of ammonium polyphosphates
0.4 part of Resorcinol
0.01 part of titanium oxide
As preferably, preparation method comprises the steps:
(1), according to said ratio, ammonium polyphosphate, Resorcinol, titanium oxide are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 240 DEG C;
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 310 DEG C;
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
Embodiment 4:
A kind of preparation method of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, described raw material comprises ammonium polyphosphate, dihydroxy compound, catalyzer, wherein, the molfraction of the each component of raw material (mole number of ammonium polyphosphate is by phosphoric acid mole number) ratio is as follows:
1.0 parts of ammonium polyphosphates
0.6 part of hexylene glycol
0.02 part of silicon oxide
As preferably, preparation method comprises the steps:
(1), according to said ratio, ammonium polyphosphate, hexylene glycol, silicon oxide are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 250 DEG C;
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 320 DEG C;
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
Embodiment 5
A kind of preparation method of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, described raw material comprises ammonium polyphosphate, dihydroxy compound, catalyzer, wherein, the molfraction of the each component of raw material (mole number of ammonium polyphosphate is by phosphoric acid mole number) ratio is as follows:
As preferably, preparation method comprises the steps:
(1), according to said ratio, ammonium polyphosphate, propylene glycol, dihydroxyphenyl propane, calcium oxide, Lithium Acetate are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 245 DEG C;
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 316 DEG C;
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
Embodiment 6:
A kind of preparation method of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, described raw material comprises ammonium polyphosphate, dihydroxy compound, catalyzer, wherein, the molfraction of the each component of raw material (mole number of ammonium polyphosphate is by phosphoric acid mole number) ratio is as follows:
As preferably, preparation method comprises the steps:
(1), according to said ratio, ammonium polyphosphate, hexylene glycol, Resorcinol, aluminum oxide, antimony glycol are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 243 DEG C;
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 318 DEG C;
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
Embodiment 7:
A kind of preparation method of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, described raw material comprises ammonium polyphosphate, dihydroxy compound, catalyzer, wherein, the molfraction of the each component of raw material (mole number of ammonium polyphosphate is by phosphoric acid mole number) ratio is as follows:
As preferably, preparation method comprises the steps:
(1), according to said ratio, ammonium polyphosphate, propylene glycol, Resorcinol, titanium oxide, antimony glycol are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 244 DEG C;
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 315 DEG C;
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
Embodiment 8:
A kind of preparation method of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, described raw material comprises ammonium polyphosphate, dihydroxy compound, catalyzer, wherein, the molfraction of the each component of raw material (mole number of ammonium polyphosphate is by phosphoric acid mole number) ratio is as follows:
As preferably, preparation method comprises the steps:
(1), according to said ratio, ammonium polyphosphate, propylene glycol, dihydroxyphenyl propane, silicon oxide, cobalt oxalate are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 246 DEG C;
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 314 DEG C;
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
Embodiment 9:
A kind of preparation method of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, described raw material comprises ammonium polyphosphate, dihydroxy compound, catalyzer, wherein, the molfraction of the each component of raw material (mole number of ammonium polyphosphate is by phosphoric acid mole number) ratio is as follows:
As preferably, preparation method comprises the steps:
(1), according to said ratio, ammonium polyphosphate, propylene glycol, dihydroxyphenyl propane, silicon oxide, cobalt oxalate are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 244 DEG C;
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 312 DEG C;
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
Embodiment 10:
A kind of preparation method of crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular, described raw material comprises ammonium polyphosphate, dihydroxy compound, catalyzer, wherein, the molfraction of the each component of raw material (mole number of ammonium polyphosphate is by phosphoric acid mole number) ratio is as follows:
As preferably, preparation method comprises the steps:
(1), according to said ratio, ammonium polyphosphate, propylene glycol, dihydroxyphenyl propane, titanium oxide, cobalt oxalate are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 242 DEG C;
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 312 DEG C;
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
In above-mentioned each comparative example and embodiment, various ammonium polyphosphates used, triphenylphosphate, dihydroxy compound, catalyzer etc., be the industrial goods of buying from market.
Each properties of sample parameter testing result is as following table 1:
The each comparative example of table 1 and each embodiment pilot sample performance parameter test result
Embodiment mean value: the various performance parameters mean value that refers to embodiment 1-10.
Can find out from the test result of table 1, ammonium polyphosphate and triphenylphosphate have a large amount of gaseous volatilization deposits yields in the time of 280 DEG C, and ammonium polyphosphate is to have produced a large amount of ammonias because it at high temperature decomposes; Triphenylphosphate is that under high temperature, liquid object volatility is large, therefore because its fusing point is low, these two kinds of fire retardants are applied under hot conditions, have a large amount of γ-ray emissions, cause by flame-retarded resin and foam, particularly ammonium polyphosphate, gas forming amount is large, decomposes violent and rapid.The present invention is cross-linked ammonium polyphosphate by polyol, slough the ammonia G&W in system simultaneously, greatly improve the resistance to elevated temperatures of phosphorus flame retardant, only had 0.98% the evenly heat weightlessness of 280 DEG C, can meet the requirement of materials processing to temperature completely.
Can find out from the test result of table 1, the solubleness in water of ammonium polyphosphate is very large, and also will ceaselessly be hydrolyzed in water, in use larger to the performance impact of material, also easily from material, separates out; Triphenylphosphate also has higher solubleness in water.The crosslinked calcium polyphosphate ester halogen-free flame retardants of a kind of high molecular that the present invention produces, its phosphorus content is between ammonium polyphosphate (phosphorus content is greater than 30%) and triphenylphosphate (phosphorus content 10.5), average out to 24.2, pass through crosslinking reaction, not only improve the heat resisting temperature of fire retardant, improve the water tolerance of fire retardant simultaneously, reduced the solubleness (average solubleness in water be 0.14%) of fire retardant in water.Can see by test data, the crosslinked calcium polyphosphate ester halogen-free flame retardants of a kind of high molecular of the present invention, in the time that phosphorus content is controlled at below 24%, has greatly improved the water tolerance of fire retardant, and the solubleness in water is lower than 0.1%.
Claims (10)
1. a crosslinked calcium polyphosphate ester halogen-free flame retardants for high molecular, is characterized in that the structural formula of this halogen-free flame retardants is
R is wherein selected from arylidene or alkylidene group.
2. the crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular according to claim 1, is characterized in that: described R group is selected from any one in following substituting group:
3. according to the crosslinked calcium polyphosphate ester halogen-free flame retardants of claim 1 or high molecular claimed in claim 2, it is characterized in that comprising following raw material:
Ammonium polyphosphate, dihydroxy compound and catalyzer;
Wherein, the molfraction of each component is as follows:
1.0 parts of ammonium polyphosphates
Dihydroxy compound 0.2-0.8 part
Catalyzer 0.001-0.06 part
The mole number of ammonium polyphosphate is by phosphoric acid mole number.
4. according to the crosslinked calcium polyphosphate ester halogen-free flame retardants of claim 1 or high molecular claimed in claim 2, it is characterized in that comprising following raw material: ammonium polyphosphate, dihydroxy compound and catalyzer; The molfraction of each component is as follows:
1.0 parts of ammonium polyphosphates
Dihydroxy compound 0.4-0.6 part
Catalyzer 0.01-0.02 part
Wherein, the mole number of ammonium polyphosphate is by phosphoric acid mole number.
5. according to the crosslinked calcium polyphosphate ester halogen-free flame retardants of claim 1 or high molecular claimed in claim 2, it is characterized in that reacting by following reaction formula:
Wherein m+n=2p.
6. according to the crosslinked calcium polyphosphate ester halogen-free flame retardants of claim 3 or high molecular claimed in claim 4, it is characterized in that: described dihydroxy compound raw material comprises ethylene glycol, propylene glycol, hexylene glycol, dihydroxyphenyl propane, the mixture of one or more in Resorcinol.
7. according to the crosslinked calcium polyphosphate ester halogen-free flame retardants of claim 3 or high molecular claimed in claim 4, it is characterized in that: described catalyzer is antimony glycol, Lithium Acetate, aluminum oxide, calcium oxide, cobalt oxalate, silicon oxide, the mixture of one or more in titanium oxide.
8. according to the crosslinked calcium polyphosphate ester halogen-free flame retardants of claim 3 or high molecular claimed in claim 4, it is characterized in that: described ammonium polyphosphate is II type long-chain ammonium polyphosphate, and the polymerization degree is greater than 1000.
9. according to a preparation method for the crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular described in claim 3 or claim 4, it is characterized in that comprising the following steps:
(1), according to said ratio, ammonium polyphosphate, dihydroxy compound, catalyzer are stirred in homogenizer;
(2) by cord wood twin screw extruder melt blending, each reactant is fully mixed, and initial reaction, slough the volatile matters such as part ammonia G&W, the temperature of forcing machine is controlled at 200-260 DEG C;
(3), completely curing in Banbury mixer or High Temperature Furnaces Heating Apparatus, crosslinked, slough remaining ammonia G&W, temperature is controlled at 280-350 DEG C;
(4) blowing, is cooled to solid mass;
(5) solid mass is pulverized, the fine powder being finally ground to more than 1000 orders obtains finished product.
10. the preparation method of the crosslinked calcium polyphosphate ester halogen-free flame retardants of high molecular according to claim 9, is characterized in that: in step (2), the temperature of forcing machine is controlled at 240-250 DEG C; The temperature of step (3) in Banbury mixer or High Temperature Furnaces Heating Apparatus is controlled at 310-320 DEG C.
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| CN111378288A (en) * | 2020-04-13 | 2020-07-07 | 联塑科技发展(贵阳)有限公司 | Flame-retardant smoke suppressant, flame-retardant smoke suppressant type PVC modified material and preparation method thereof |
| CN115842125A (en) * | 2022-01-06 | 2023-03-24 | 宁德时代新能源科技股份有限公司 | Positive electrode material and preparation method and application thereof |
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| CN108641091B (en) * | 2018-04-24 | 2021-03-30 | 利尔化学股份有限公司 | Polymethyl ethylene glycol hypophosphite aluminum salt and preparation method and application thereof |
| CN111378288A (en) * | 2020-04-13 | 2020-07-07 | 联塑科技发展(贵阳)有限公司 | Flame-retardant smoke suppressant, flame-retardant smoke suppressant type PVC modified material and preparation method thereof |
| CN115842125A (en) * | 2022-01-06 | 2023-03-24 | 宁德时代新能源科技股份有限公司 | Positive electrode material and preparation method and application thereof |
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